Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides

ABSTRACT

Compounds of the formula ##STR1## wherein R is halogen, C 1  -C 4  alkoxy, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, cyano, nitro, S(O) n  R wherein R is C 1  -C 4  alkyl and n is the integer 0, 1 or 2; and R 2  through R 8  are hydrogen or certain substituents, their salts, herbicidal compositions containing the compound or salts and the herbicidal use thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of Ser. No.772,593, filed Sept. 5, 1985 now abandoned; which in turn is acontinuation-in-part application of Ser. No. 634,408, filed July 31,1984, now abandoned; which in turn is a continuation-in-part applicationof Ser. No. 587,331, filed Mar. 7, 1984, now abandoned; which in turn isa continuation-inpart of application Ser. No. 532,869, filed Sept. 16,1983, now abandoned; which in turn is a continuation-in-part applicationof Ser. No. 464,251, filed Feb. 9, 1983, now abandoned; which in turn isa continuation-in-part application of Ser. No. 361,658, filed Mar. 25,1982, now abandoned.

Applicants specifically incorporate by reference the contents of theabove listed U.S. patent applications.

BACKGROUND OF THE INVENTION

Compounds having the structural formula ##STR2## wherein X can be alkyl,n can be 0, 1, or 2, and R₁ can be phenyl or substituted phenyl aredescribed in Japanese Patent Application No. 84632-1974 as beingintermediates for the preparation of herbicidal compounds of the formula##STR3## wherein R₁, X, and n are as defined above and R₂ is alkyl,alkenyl, or alkynyl. Specifically taught herbicidal compounds of thislatter group are those where n is 2, X is 5,5-dimethyl, R₂ is allyl andR₁ is phenyl, 4-chlorophenyl or 4-methoxyphenyl.

The precursor intermediates for these three specifically taughtcompounds have no or almost no herbicidal activity.

DESCRIPTION OF THE INVENTION

Embodiment A of this invention relates to certain novel 2-(2-substitutedbenzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of thisembodiment have the following structural formula ##STR4## wherein R andR¹ are hydrogen, C₁ -C₄ alkyl, preferably methyl or isopropyl, R^(a)OC(O)--, where R^(a) is C₁ -C₄ alkyl; most preferably R and R¹ arehydrogen;

R² is chlorine, bromine, iodine or C₁ -C₄ alkoxy, preferably methoxy;most preferably R₂ is chlorine, bromine or methoxy;

R³, R⁴ and R⁵ independently are hydrogen or an aliphatic group,preferably: (1) hydrogen; (2) halogen, preferably chlorine or bromine;(3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferablymethoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- whereinR^(b) is C₁ -C₄ alkyl, preferably methyl, C₁ -C₄ haloalkyl, phenyl,benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently arehydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2, preferably 2;##STR5## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen or C₁ -C₄alkyl, preferably methyl; (11) R^(f) C(O) wherein R^(f) is hydrogen, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; (12) --NR^(g) R^(h) whereinR^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; or lesspreferably (13) R³ and R⁴ together can form a ring structure with twoadjacent carbon atoms of the phenyl ring.

R³ and R⁴ can also be (14) C₃ -C₅ alkenyloxy (thio) optionallysubstituted, preferably with halogen or (15) C₃ -C₅ alkynyloxy (thio),optionally substituted, preferably with halogen.

Most preferably, R³ is chlorine, hydrogen, dimethylamino or methoxy.Preferably, R⁴ is hydrogen, chlorine, nitro, SO₂ CH₃, SO₂ N(CH₃)₂ ortrifluoromethyl. Preferably, R⁵ is hydrogen.

Embodiment A' of this invention is an herbicidal composition comprisingan herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inertcarrier threfor. Preferably, the 2-position of the benzoyl moiety issubstituted with chlorine, bromine, iodine or C₁ -C₄ alkoxy; morepreferably chlorine, bromine or methoxy; most preferably chlorine. The5-position of the 1,3-cyclohexanedione moiety can be substituted withone or two C₁ -C₄ alkyl groups, preferably methyl, although such asubstitution is not preferred.

The compounds of Embodiment A of this invention can have the followingfour structural formulae because of tautomerism: ##STR6## wherein R, R¹,R², R³, R⁴ and R⁵ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR7## whereinR, R¹, R², R³, R⁴ and R⁵ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals, e.g. lithium, sodium, and potassium, alkaline earth metals, e.g.barium, magnesium, calcium and strontium or organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substituentis an aliphatic or aromatic group.

In the above description of the compounds of this invention, alkyl andalkoxy include both straight and branched configurations; for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, andtert-butyl.

Embodiment B of this invention relates to certain novel 2-(2-substitutedbenzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of thisembodiment have the following structural formula ##STR8## wherein R¹⁰ isC₁ -C₆ alkyl, preferably C₁ -C₄, more preferably methyl;

R¹¹ is hydrogen or C₁ -C₆ alkyl, preferably C₁ -C₄, more preferablymethyl or ##STR9## wherein R^(a) is C₁ -C₄ alkyl or R¹⁰ and R¹¹ togetherare alkylene having 3 to 6 carbon atoms, most preferably R¹¹ is hydrogenor methyl;

R¹² is chlorine, bromine, iodine, fluorine or C₁ -C₄ alkoxy, preferablymethoxy; most preferably R¹² is chlorine, bromine or methoxy;

R¹³ and R¹⁴ independently are (1) hydrogen or an aliphatic group,preferably hydrogen; (2) halogen, preferably, fluorine, chlorine orbromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ aliphaticalkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro;(8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n)-- wherein R^(b) is C₁ -C₄ alkyl, preferably methyl, C₁ -C₄ haloalkyl,phenyl, benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently arehydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2, preferably 2;##STR10## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen or C₁ -C₄alkyl, preferably methyl; (11) R^(f) C(O) wherein R^(f) is hydrogen, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; (12) --NR^(g) R^(h) whereinR^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; (13) C₁ -C₄alkylthio or less preferably (14) R¹³ and R¹⁴ together can form a ringstructure with two adjacent carbon atoms of the phenyl ring to whichthey are attached or less preferably (15) R¹³ and R¹⁴ are the groupsphenoxy or substituted phenoxy wherein the substituent is halogen orhalomethyl or both;

R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are independently the same or different and areselected from the group consisting of hydrogen, C₁ -C₆ alkyl, preferablyC₁ -C₄ alkyl, more preferably methyl, most preferably hydrogen ormethyl, and their salts;

provided, however, that R¹⁵ and R¹⁶ together may form a substituted orunsubstituted alkylene ring of 2-5 carbon atoms, the preferredsubstituent being 1 or 2 methyl groups.

More preferably, R¹³ is chlorine, hydrogen, methyl, alkylthio ormethoxy. Preferably R¹⁴ is hydrogen, chlorine, nitro, trifluoromethyl,or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl, preferably methyl and nis the integer 0, 1 or 2, preferably 2.

The compounds of Embodiment B of this invention can have the followingfour structural formulae because of tautomerism: ##STR11## wherein R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR12## whereinR¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium, alkaline earth metals, e.g.barium, magnesium, calcium and strontium, or organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substitutentis an aliphatic or aromatic group.

The term "aliphatic group" is used form Embodiments A and B herein in abroad sense to cover a large class of organic groups characterized bybeing derived from (1) an acylic (open-chain structure) of the paraffin,olefin and acetylene hydrocarbon series and their derivatives or (2)alicyclic compounds. The aliphatic group can have from 1 to 10 carbonatoms.

The term "aromatic group" is used for Embodiments A and B herein in abroad sense to distinguish from the aliphatic group and includes a groupderived from (1) compounds having 6 to 20 carbon atoms and characterizedby the presence of at least one benzene ring, including monocyclic,bicyclic and polycyclic hydrocarbons and their derivatives and (2)heterocyclic compounds having 5 to 19 carbon atoms which are similar instructure and are characterized by having an unsaturated ring structurecontaining at least one atom other than carbon such as nitrogen, sulfurand oxygen and derivatives of these heterocyclic compounds.

In the above description of the compounds of this invention alkyl andalkoxy include both straight and branched configurations; for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, andtert-butyl.

Embodiment C of this invention relates to certain novel2-(2'-cyanobenzoyl)cyclohexane-1,3-diones as herbicides. The compoundsof of this embodiment have the following structural formula ##STR13##wherein R²¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R²¹ is hydrogen or methyl;

R²² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR14## wherein R^(a) is C₁ -C₄ alkyl, most preferably R²²is hydrogen or methyl; or R²¹ and R²² together are alkylene having 3 to6 carbon atoms;

R²³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R²³ is hydrogen or methyl;

R²⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R²⁴ is hydrogen or methyl;

R²⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R²⁵ is hydrogen or methyl;

R²⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R²⁶ is hydrogen;

R²⁷ and R²⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl;

(4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano;(7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9)R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl;

(11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or

(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, with theproviso that R²⁷ is not attached to the 6-position.

Preferably, R²⁷ is in the 3-position. Most preferably R²⁷ is hydrogenand R²⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, orR^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this embodiment can have the following four structuralformulae because of tautomerism: ##STR15## wherein R²¹, R²², R²³, R²⁴,R²⁵, R²⁶, R²⁷ and R²⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR16## whereinR²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are as defined above.

Examples of cations of these bases are inorgaic cations such as alkalimetals e.g. lithium, sodium, and potassium organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substitutentis an aliphatic or aromatic group.

Embodiment D of this invention relates to2-(2-nitrobenzoyl)-1,3-cyclohexanediones and their use as herbicides.

The compounds have a nitro substitution in the 2-position of the phenylmoiety of their compounds. The nitro substitution imparts exceptionalherbicidal activity to the compounds of this invention.

Embodiment D' of this invention is an herbicidal composition comprisingan herbicidally active 2-(2-nitrobenzoyl)-1,3-cyclohexanedione and aninert carrier therefor. The 4-, 5- and 6-positions of the1,3-cyclohexanedione moiety can be substituted, preferably with thegroups hereinafter recited. More preferably, the 1,3-cyclohexanedionemoiety has no substitution or the 4- or 6-positions are substituted withone or two methyl groups. The 3-, 4- and 5-positions of the benzoylmoiety can be substituted, preferably with the groups hereinafterrecited.

The novel compounds of Embodiment D have the following structuralformula ##STR17## wherein R³¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁-C₂ alkyl, more preferably methyl, most preferably R³¹ is hydrogen ormethyl;

R³² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR18## wherein R^(a) is C₁ -C₄ alkyl, most preferably R³²is hydrogen or methyl; or

R³¹ and R³² together are alkylene having 3 to 6 carbon atoms;

R³³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R³³ is hydrogen or methyl;

R³⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R³⁴ is hydrogen or methyl;

R³⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R³⁵ is hydrogen or methyl;

R³⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R³⁶ is hydrogen;

R³⁷ and R³⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl;

(11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or

(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, with theproviso that R³⁷ is not attached to the 6-position.

Preferably, R³⁷ is in the 3-position. Most preferably R³⁷ is hydrogen orC₁ -C₄ alkoxy and R³⁸ is hydrogen, chlorine, bromine, fluorine,trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferablymethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkylgroups with one or more hydrogens replaced by chlorine, bromine, iodineor fluorine.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR19## wherein R³¹, R³², R³³, R³⁴,R³⁵, R³⁶, R³⁷ and R³⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR20## whereinR³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium or organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substitutentis an aliphatic or aromatic group.

Embodiment E of this invention relates to2-(2-benzoyl)-1,3-cyclohexanediones and their use as herbicides.

Embodiment E' of this invention is an herbicidal composition comprisingan herbicidally active 2-(2-C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl or C₁-C₄ alkylsulfonyl benzoyl)-1,3-cyclohexanedione and an inert carriertherefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moietycan be substituted, preferably with the groups hereinafter recited. Morepreferably, the 1,3-cyclohexanedione moiety has no substitution or the4- or 6-positions are substituted with one or two methyl groups. The 3-,4- and 5-positions of the benzoyl moiety can be substituted, preferablywith the groups hereinafter recited.

The novel compounds of Embodiment E have the structural formula##STR21## wherein n is the integer 0, 1 or 2, preferably 2;

R⁴⁰ is C₁ -C₄ alkyl, preferably methyl;

R⁴¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁴¹ is hydrogen or methyl;

R⁴² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR22## wherein R^(a) is C₁ -C₄ alkyl, most preferably R⁴²is hydrogen or methyl; or

R⁴¹ and R⁴² together are alkylene having 3 to 6 carbon atoms;

R⁴³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁴³ is hydrogen or methyl;

R⁴⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁴⁴ is hydrogen or methyl;

R⁴⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁴⁵ is hydrogen or methyl;

R⁴⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁴⁶ is hydrogen;

R⁴⁷ and R⁴⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are asdefined, with the proviso that R⁴⁷ is not attached to the 6-position.

Preferably, R⁴⁷ is in the 3-position. Most preferably R⁴⁷ is hydrogen or3-chlorine and R⁴⁸ is hydrogen, chlorine, bromine, fluorine,trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferablymethyl.

The term "C₁ -C₄ " alkyl includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkylgroups with one or more hydrogens replaced by chloro, bromo, iodo orfluoro.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR23## wherein n, R⁴⁰, R⁴¹, R⁴²,R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR24## whereinn, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium, organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substitutentis an aliphatic or aromatic group.

Embodiment F of this invention relates to2-(2-alkylbenzoyl)-1,3-cyclohexanediones and their use as herbicides.

Embodiment F' of this invention is an herbicidal composition comprisingan herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inertcarrier therefor wherein the 2-position of the benzoyl moiety issubstituted with C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, optionallysubstituted with halogen, more preferably methyl or trifluoromethyl andthe 4-position preferably is substituted with an electron withdrawinggroup, such as halogen, cyano, trifluoromethyl or nitro. The 4-, 5- and6-positions of the 1,3-cyclohexanedione moiety can be substituted,preferably with the groups hereinafter recited. More preferably, the1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positionsare substituted with one or two methyl groups. The 3-, 4- and5-positions of the benzoyl moiety can be substituted, preferably withthe groups hereinafter recited.

The novel compounds of Embodiment F have the following structuralformula ##STR25## wherein R⁵⁰ is C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl,optionally substituted with halogen, more preferably methyl andtrifluoromethyl;

R⁵¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁵¹ is hydrogen or methyl;

R⁵² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR26## wherein R^(a) is C₁ -C₄ alkyl, most preferably R⁵²is hydrogen or methyl; or

R⁵¹ and R⁵² together are alkylene having 3 to 6 carbon atoms;

R⁵³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁵³ is hydrogen or methyl;

R⁵⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁵⁴ is hydrogen or methyl;

R⁵⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁵⁵ is hydrogen or methyl;

R⁵⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁵⁶ is hydrogen;

R⁵⁷ and R⁵⁸ independently are (1) hydrogen; (2) halogen; preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are asdefined, with the proviso that R⁵⁷ is not attached to the 6-position.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkylgroups with one or more hydrogens replaced by chloro, bromo, iodo orfluoro.

Preferably, R⁵⁷ is in the 3-position. Most preferably R⁵⁷ is hydrogenand R⁵⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, orR^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR27## wherein R⁵⁰, R⁵¹, R⁵², R⁵³,R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷ and R⁵⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR28## whereinR⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷ and R⁵⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substituentis an aliphatic or aromatic group.

Embodiment G of this invention relates to2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.

Embodiment G' of this invention is an herbicidal composition comprisingan herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione andan inert carrier therefor. The 4- and 6-positions of the1,3,5-cyclohexanetrione moiety are preferably substituted with groupshereinafter defined, most preferably with all methyl groups. The benzoylmoiety can be substituted, preferably with the groups hereinafterrecited.

The novel compounds of Embodiment G have the following structuralformula ##STR29## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl,preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁-C₂ haloalkyl, preferably trifluoromethyl; R^(a) SO_(n) -- wherein n is0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl,trifluoromethyl or difluoromethyl; or trifluoromethoxy ordifluoromethoxy. Preferably, R⁶⁰ is chlorine, bromine, C₁ -C₂ alkyl, C₁-C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethylor methylsulfonyl; and

R⁶¹ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁶² is hydrogen or C₁ -C₄ alkyl, preferably methyl; or

R⁶¹ and R⁶² together are C₂ -C₅ alkylene;

R⁶³ is C₁ -C₄ alkyl, preferably methyl;

R⁶⁴ is C₁ -C₄ alkyl, preferably methyl; or

R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene;

R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are asdefined; or (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are asdefined.

Preferably R⁶⁵ is in the 3-position. More preferably R⁶⁵ is hydrogen,chlorine, fluorine, trifluoromethyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄thioalkyl. Most preferably, R⁶⁵ is hydrogen. Preferably R⁶⁶ is in the4-position. Most preferably R⁶⁶ is halogen, cyano, trifluoromethyl, orR^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, n-butoxy, sec-butoxy, isobutoxy andt-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups definedabove under C₁ -C₄ alkyl in which one or more hydrogens is replaced bychlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) areincluded within the scope of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR30## wherein R⁶⁰, R⁶¹, R⁶², R⁶³,R⁶⁴, R⁶⁵ and R⁶⁶ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by reaction with a base toform a salt having an anion of the following four resonance forms:##STR31## wherein R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are as definedabove.

Examples of cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals,e.g. calcium and magnesium or ammonium or organic cations such assubstituted ammonium, sulfonium, sulfoxonium or phosphonium wherein thesubstituents are aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of thisinvention that varying degress os association between the anion andcation will exist depending upon the nature of the cation. In someinstances with a suitable cation, such as copper, the salt can exist ina chelated form.

The compounds of this invention and their salts are active herbicides ofa general type. That is, they are herbicidally effective against a widerange of plant species. The method of controlling undesirable vegetationof the present invention comprises applying an herbicidally effectiveamount of the above-described compounds to the area where control isdesired.

The compounds of Embodiments A and A' of the present invention can beprepared by the following general method. ##STR32##

Generally, mole amounts of the dione and substituted benzoyl cyanide areused, along with a slight mole excess of zinc chloride. The tworeactants and the zinc chloride are combined in a solvent such asmethylene chloride. A slight mole excess of triethylamine is slowlyadded to the reaction mixture with cooling. The mixture is stirred atroom temperature for 5 hours.

The reaction product is worked up by conventional techniques.

The above-described substituted benzoyl cyanide can be preparedaccording to the teaching of T. S. Oakwood and C. A. Weisgerber, OrganicSynthesis Collected, Vol. III, pp. 122 (1955).

The following example teaches the synthesis of a representative compoundof Embodiments A and A' of this invention.

EXAMPLE 1-A, A' 2-(2,4-Dichlorobenzoyl)-cyclohexane-1,3-dione ##STR33##

1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole),2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powderedzinc chloride were combined in 100 milliliters (ml) methylene chloride.Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. Thereaction mixture was stirred at room temperature for 5 hours and thenpoured into 2N hydrochloric acid. The aqueous phase was discarded andthe organic phase was washed with 150 ml 5% Na₂ CO₃ four times. Theaqueous washings were combined and acidified with HCl, extracted withmethylene chloride, dried and concentrated to yield 25.3 g of crudeproduct. The crude product was dissolved in ether and stirred with 250ml of 5% copper (II) acetate. The resulting copper salt was filtered,washed with ether and stirred with 6N hydrochloric acid to destroy thesalt. The extract was washed with ether to yield 22.15 grams of thedesired product m.p. 138°-140° C. (77.7% yield). The structure wasconfirmed by instrumental analysis.

The compounds of Embodiment B of the present invention can be preparedby the following general method. ##STR34##

Generally, mole amounts of the dione and substituted benzoyl cyanide areused, along with a slight mole excess of zinc chloride. The tworeactants and the zinc chloride are combined in a solvent such asmethylene chloride. A slight mole excess of triethylamine is slowlyadded to the reaction mixture with cooling. The mixture is stirred atroom temperature for 5 hours.

The reaction product is worked up by conventional techniques.

The above-described substituted benzoyl cyanide can be preparedaccording to the teaching of T. S. Oakwood and C. A. Weisgerber, OrganicSynthesis Collected, Vol. III, pp. 122 (1955).

The following example teaches the synthesis of a representative compoundof Embodiment B of this invention.

EXAMPLE 1-B 4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione##STR35##

4,4-Dimethyl-1,3-cyclohexanedione [14.0 grams (g), 0.1 mole], 20.0 g(0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous,powdered zinc chloride were combined in 100 milliliters (ml) methylenechloride. Triethylamine (10.1 g, 0.12 mole) was slowly added withcooling. The reaction mixture was stirred at room temperature for 5hours and then poured into 2N hydrochloric acid. The aqueous phase wasdiscarded and the organic phase was washed with 150 ml 5% Na₂ CO₃ fourtimes. The aqueous washings were combined and acidified with HCl,extracted with methylene chloride, dried and concentrated to yield 25.3g of crude product. The crude product was chromatographed (2% AcOH/CH₂Cl₂) in 5 g aliquots then reduced on rotavap under reduced pressure at50° C. for 30 minutes to remove AcOH. This yielded an oil (40% yield).The structure was confirmed by instrumental analysis.

The compounds of Embodiment C of the present invention can be preparedby the following general method. ##STR36##

Generally, in step (1) mole amounts of the dione and substituted benzoylchloride are used, along with a slight mole excess of triethylamine. Thetwo reactants are combined in a solvent such as methylene chloride. Thetriethylamine is slowly added to the reaction mixture with cooling. Themixture is stirred at room temperature for several hours.

The reaction product is worked up by conventional techniques. ##STR37##

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the triethylamine, preferably 2 moles of thetriethylamine and up to 0.5 mole, preferably 0.1 mole of a cyanidesource (e.g., potassium cyanide or acetone cyanohydrin). The mixture isstirred in a reaction pot for about one hour at room temperature and thedesired product is recovered by conventional techniques.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR38## wherein R²⁷ and R²⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are two representative examples of the methods describedtherein. ##STR39## wherein R²⁷ and R²⁸ are as previously defined.

In reaction (a) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR40## wherein R²⁷ and R²⁸ are as previously defined.

In reaction (b) the substituted toluene is heated to reflux in anaqueous solution of potassium permanganate for several hours. Thesolution is then filtered and the reaction product is isolated byconventional techniques.

The following example teaches the synthesis of a representative compoundof Embodiment C of this invention.

EXAMPLE 1-C 2-(2'-Cyanobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione##STR41##

2-Cyanobenzoyl chloride (3.9 g, 24 mmol) and4,4-dimethyl-1,3-cyclohexanedione (3.3 g, 24 mmol) were dissolved in 75ml methylene chloride. Triethylamine (5.0 ml, 36 mmol) was addeddropwise and the resulting solution stirred for one and one-half hoursat room temperature. The solution was washed with water, 2 normalhydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K₂ CO₃)and saturated sodium chloride solution (brine), dried over anhydrousmagnesium sulfate (MgSO₄) and concentrated under vacuum. The residue wasdissolved in 20 ml acetonitrile. Triethylamine (4.4 ml, 32 mmol) andacetone cyanohydrin (5 drops) were added and the solution stirred fortwo hours. After dilution with ether, the solution was washed with 2NHCl and extracted with 5% K₂ CO₃. The aqueous extract was acidified withconcentrated hydrochloric acid and extracted with ether. The ether waswashed with water and brine, dried (MgSO₄) and concentrated undervacuum. The residue was purified by silica gel chromatography, yielding1.2 g of a viscous oil which was identified as the desired compound bynuclear magnetic resonance spectroscopy, infrared spectroscopy and massspectroscopy.

The compounds of Embodiments D and D' of the present invention can beprepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR42## wherein R³¹ through R³⁸ andmoderate base are as defined and X is halogen, preferably chlorine, C₁-C₄ alkyl--C(O)--O--, C₁ -C₄ alkoxy--C(O)--O-- or ##STR43## wherein R³⁷and R³⁸ in this portion of the molecule are identical with those in thereactant shown above and the moderate base is as defined, preferablytri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoylreactant are used, along with a mole amount or excess of the base. Thetwo reactants are combined in an organic solvent such as methylenechloride, toluene, ethyl acetate or dimethylformamide. The base orbenzoyl reactant preferably are added to the reaction mixture withcooling. The mixture is stirred at 0° C.-50° C. until the reaction issubstantially complete. ##STR44## wherein the moderate base and R³¹through R³⁸ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the base, preferably about 2 moles of moderate baseand from 0.01 mole to about 0.5 mole or higher, preferably around 0.1mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 50° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl)silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases such astertiary amines and inorganic bases such as alkali metal carbonates andphosphates. Suitable tertiary amines include trialkylamines such astriethylamine. Suitable inorganic bases include potassium carbonate andtrisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the Crownethers.

A number of different solvents may be usable in this process, dependingon the nature of the acid chloride or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangement may be conducted at temperatures up to about50° C.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, po.767-769 (1967). ##STR45## wherein R³⁷ and R³⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are three representative examples of the methods describedtherein. ##STR46## wherein R³⁷ and R³⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR47##wherein R³⁷ and R³⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR48## wherein R³⁷ and R³⁸ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in anaqueous solution of potassium permanganate for several hours. Thesolution is then filtered and the reaction product is isolated byconventional techniques.

The following examples teach the synthesis of representative compoundsof Embodiment D and D' of this invention.

EXAMPLE 1-D,D' 2-(2'-Nitrobenzoyl)-1,3-cyclohexanedione ##STR49##

2-Nitrobenzoyl chloride (5.0 g, 27 mmol) and cyclohexanedione (3.0 g, 27mmol) were dissolved in methylene chloride. Triethylamine (4.9 ml, 35mmol) was added dropwise and the resulting solution stirred for onehour. The solution was washed with 2 normal hydrochloric acid (2N HCl),water, 5% potassium carbonate solution and saturated sodium chloridesolution, dried over anhydrous magnesium sulfate (MgSO₄) andconcentrated under vacuum. The residue was dissolved in 20 mlacetonitrile. Triethylamine (1 equivalent) and potassium cyanide (40 mol%) were added and the solution stirred for one hour at room temperature.After dilution with ether, the solution was washed with 2N HCl andextracted with 5% potassium carbonate solution. The aqueous extract wasacidified and ether was added. Filtration of the resulting mixtureyielded 3.2 g of the desired compound (m.p. 132°-135° C.) which wasidentified by nuclear magnetic resonance spectroscopy, infraredspectroscopy and mass spectroscopy.

EXAMPLE 2-D,D' 2-(2'-Nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione##STR50##

Triethylamine (3.4 ml, 25 mmol) was added dropwise to a methylenechloride solution of 2-nitrobenzoyl chloride (3.5 g, 19 mmol) and5,5-dimethylcyclohexanedione (2.4 g, 19 mmol). After stirring for onehour at room temperature an additional 3 equivalents of triethylamineand 0.4 ml acetone cyanohydrin were added. The solution was stirred for2.5 hours, then washed with 2N HCl and extracted with 5% potassiumcarbonate solution. The basic extracts were acidified with 2N HCl andextracted with ether. The ether portion was washed with saturated sodiumchloride solution, dried over anhydrous magnesium sulfate andconcentrated under vacuum. The residue was recrytallized from ethylacetate yielding 2.0 g of the desired compound (m.p. 130°-133° C.) whichwas identified as such by nuclear magnetic resonance spectroscopy,infrared spectroscopy and mass spectroscopy.

The compounds of Embodiments E and E' of the present invention can beprepared by the following two or three step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR51## wherein moderate base, and R⁴⁰through R⁴⁸ are defined herein, and X is halogen, preferably chlorine,C₁ -C₄ alkyl--C(O)--O--, C₁ -C₄ alkoxy--C(O)--O-- or ##STR52## whereinR⁴⁰, R⁴⁷ and R⁴⁸ in this portion of the moledule are identical withthose in the reactant shown above, and the moderate base is as defined,preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metalphosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoylreactant are used, along with a mole amount or excess of the base. Thetwo reactants are combined in an organic solvent such as methylenechloride, toluene, ethyl acetate or dimethylformamide. The base orbenzoyl reactant preferably are added to the reaction mixture withcooling. The mixture is stirred at 0° C.-50° C. until the reaction issubstantially complete. ##STR53##

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the base, preferably about 2 moles of moderate baseand from 0.01 mole to about 0.5 mole or higher, preferably around 0.1mole of the cyanide source (e.g., potassium cyanide oracetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 50° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl)silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases such astertiary amines and inorganic bases such as alkali metal carbonates andphosphates. Suitable tertiary amines include trialkylamines such astriethylamine. Suitable inorganic bases include potassium carbonate andtrisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the Crownethers.

A number of different solvents may be usable in this process, dependingon the nature of the acid chloride or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangement may be conducted at temperatures up to about50° C. ##STR54## wherein n is 1 or 2.

Generally in step (3), a mole of the reaction product of step (2) isreacted with a slight mole or two mole excess of of an oxidizing agentsuch as m-chloroperbenzoic acid after being dissolved in a solvent suchas methylene chloride. After completion of the reaction, the resultingmixture is stripped under vacuum. The residue is purified by silica gelchromatography to yield the desired product.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR55## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previouslydefined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are three representative examples of the methods describedtherein. ##STR56## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR57##wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR58## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as defined and X is chlorine,bromine or iodine.

In reaction (c) the substituted aromatic halide is allowed to react withmagnesium in a solvent such as ether. The solution is then poured overcrushed dry ice and the benzoic acid is isolated by conventionaltechniques.

The following examples teach the synthesis representative compounds ofEmbodiments E and E' of this invention.

EXAMPLE 1-E,E'2-(2'-Methylthiobenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR59##

2-Methylthiobenzoyl chloride (7.2 g, 39 mmol) and4,4,6-trimethylcyclohexanedione (5.0 g, 39 mmol) were dissolved inmethylene chloride. Triethylamine (7.0 ml, 50 mmol) was added dropwiseand the resulting solution stirred for one hour at room temperature. Thesolution was washed with 2 normal hydrochloric acid (2N HCl), 5%potassium carbonate solution (5% K₂ CO₃) and saturated sodium chloridesolution (brine), dried over anhydrous magnesium sulfate (MgSO₄) andconcentrated under vacuum. The residue was dissolved in 20 mlacetonitrile. Triethylamine (2.5 equivalents) and acetone cyanohydrin(0.4 ml) were added and the solution stirred for 45 minutes at roomtemperature. After dilution with ether, the solution was washed with 2NHCl and extracted with 5% K₂ CO₃. The aqueous extract was acidified withhydrochloric acid and extracted with ether. The ether was washed withbrine, dried (MgSO₄) and concentrated under vacuum. The residue waspurified by trituration with ether, yielding 5.0 g of a viscous oilwhich was identified as the desired compound by nuclear magneticresonance spectroscopy (nmr), infrared spectroscopy (ir) and massspectroscopy (ms).

EXAMPLE 2-E,E'2-(2'-Methanesulfonylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione##STR60##

The benzoyl cyclohexanedione prepared in Example 1 (2.5 g, 7.9 mmol) wasdissolved in 40 ml methylene chloride. m-Chloroperbenzoic acid (3.5 g,16 mmol) was added and the resulting solution was stirred for 45minutes. The solution was concentrated under vacuum. Purification of theresidue by silica gel chromatography yielded 1.7 g of a viscous oilwhich was identified as the desired compound by nmr, ir and ms.

EXAMPLE 3-E,E'2-(4'-Trifluoromethyl-2'-methanesulfinylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione##STR61##

2-(4'-Trifluoromethyl-2'-methylthiobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione(5.0 g, 14 mmol) (which was prepared according to the method ofExample 1) was dissolved in 50 ml methylene chloride. A solution ofm-chloroperbenzoic acid (2.4 g--80%, 14 mmol) in 50 ml methylenechloride was added dropwise and the resulting solution was stirred forthree hours at room temperature. After concentration under vacuum, theresidue was dissolved in ether and washed with 1% hydrochloric acid. A5% copper(II) acetate solution was added to the ether fraction, followedby hexane. The liquid phase was decanted and the remaining gummy solidstirred with 6N HCl and ether. The ether layer was dried (MgSO₄) andconcentrated to give 4.7 of a thick yellow solid. Purification on acentrifugally accelerated thin layer chromatograph (4 mm silica gel,50:50:1 hexane:ethyl acetate:acetic acid-eluent) yielded 2.4 g of aviscous oil which was identified as the desired compound by nmr, ir andms.

The compounds of Embodiments F and F' of the present invention can beprepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR62## wherein R⁵⁰ through R⁵⁸ are asdefined and X is halogen, preferably chlorine, C₁ -C₄ alkyl--C(O)--O--,C₁ -C₄ alkoxy--C(O)--O-- or ##STR63## wherein R⁵⁰, R⁵⁷ and R⁵⁸ in thisportion of the molecule are identical with those in the reactant shownabove and the moderate base is as defined, preferably tri-C₁ -C₆alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoylreactant are used, along with a mole amount or excess of the base. Thetwo reactants are combined in an organic solvent such as methylenechloride, toluene, ethyl acetate or dimethylformamide. The base orbenzoyl reactant preferably are added to the reaction mixture withcooling. The mixture is stirred at 0° C.-50° C. until the reaction issubstantially complete.

The reaction product is worked up by conventional techniques. ##STR64##wherein R⁵⁰ through R⁵⁸ are as defined.

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the base, preferably about 2 moles of moderate baseand from 0.01 mole to about 0.5 mole or higher, preferably around 0.1mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 80° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases such astertiary amines and inorganic bases such as alkali metal carbonates andphosphates. Suitable tertiary amines include trialkylamines such astriethylamine. Suitable inorganic bases include potassium carbonate andtrisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the Crownethers.

A number of different solvents may be usable in this process, dependingon the nature of the acid chloride or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethyl formamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangement may be conducted at temperatures up to about50° C.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR65## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previouslydefined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are four representative examples of the methods describedtherein. ##STR66## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR67##wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction is isolated by conventional techniques. ##STR68##wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as defined and X is chlorine, bromine oriodine.

The substituted aromatic halide is allowed to react with magnesium in asolvent such as ether. The solution is then poured over crushed dry iceand the benzoic acid is isolated by conventional techniques.

The following example teachs the synthesis of a representative compoundof Embodiments F and F' of this invention.

EXAMPLE 1-F,F'2-(4'-Bromo-2'-trifluoromethylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione##STR69##

4-Bromo-2-trifluoromethylbenzoyl chloride (4.3 g, 15 mmol) and4,4,6-trimethyl-1,3-cyclohexanedione (2.3 g, 15 mmol) were dissolved in100 ml methylene chloride. The solution was cooled with an ice bath andtriethylamine (2.1 ml, 15 mmol) in 10 ml methylene chloride was addeddropwise. The ice bath was then removed and the resulting solutionstirred for 30 minutes at room temperature. The solution was washed with2N hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K₂CO₃) and saturated sodium chloride solution (brine), dried overanhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. Theresidue (5.1 g) was dissolved in 20 ml acetonitrile. Triethylamine (3.5ml, 25 mmol) and 0.4 ml acetone cyanohydrin were added and the solutionstirred for two hours at room temperature while protected by a dryingtube (calcium sulfate). After dilution with ether, the solution waswashed with 2N HCl and extracted with 5 % K₂ CO₃. The aqueous extractwas acidified with concentrated hydrochloric acid and extracted withether. The ether was washed with brine, dried (MgSO₄) and concentratedunder vacuum. The resulting oil was purified on a silica gel column(80:20:1 hexane:ethyl acetate:acetic acid-eluent), yielding 1.5 g of aviscous oil which was identified as the desired compound by nuclearmagnetic resonance spectroscopy, infrared spectroscopy and massspectroscopy.

The compounds of Embodiment G and G' of the present invention can beprepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR70## wherein R⁶⁰ through R⁶⁶ andmoderate base are as defined and X is halogen, preferably chlorine, C₁-C₄ alkyl-C(O)--O--, C₁ -C₄ alkoxy-C(O)--O-- or ##STR71## wherein R⁶⁰,R⁶⁵ and R⁶⁶ in this portion of the molecule are identical with those inthe reactant shown above and the moderate base is as defined, preferablytri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the trione and substitutedbenzoyl reactant are used, along with a mole amount or excess of thebase. The two reactants are combined in an organic solvent such asmethylene chloride, toluene, ethyl acetate or dimethylformamide. Thebase or benzoyl reactant preferably is added to the reaction mixturewith cooling. The mixture is stirred at 0° C.-50° C. until the reactionis substantially complete. ##STR72## wherein the moderate base and R⁶⁰through R⁶⁶ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the moderate base, preferably about 2 moles ofmoderate base and from 0.01 mole to about 0.5 mole or higher, preferablyabout 0.1 mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 50° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases, e.g.,trialkylamines such as triethylamine and inorganic bases such as alkalimetal carbonates and phosphates. Suitable inorganic bases includepotassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the crownethers.

A number of different solvents are useful in this process, depending onthe nature of the acid halide or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangement may be conducted at temperatures up to about50° C.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR73## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previouslydefined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are three representative examples of the methods describedtherein. ##STR74## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR75##wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR76## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in anaqueous solution of potassium permanganate for several hours. Thesolution is then filtered and the reaction product is isolated byconventional techniques.

The following example teaches the synthesis of a representative compoundof Embodiment G and G' of this invention.

EXAMPLE 1-G,G'2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione##STR77##

2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) weredissolved in methylene chloride. Triethylamine was added and theresulting solution stirred at room temperature for 30 minutes. Thesolution was washed with 1 normal hydrochloric acid (1N HCl), andsaturated sodium chloride (brine), dried over anhydrous magnesiumsulfate (MgSO₄) and concentrated under vacuum. The residue was dissolvedin 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetonecyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirredat room temperature for 4 hours. After dilution with ether, the solutionwas washed with 1N HCl and extracted with 5% K₂ CO₃. The basic extractwas acidified with HCl and extracted with ether. The ether extract waswashed with brine, dried over MgSO₄ and concentrated under vacuum,yielding 2.2 g of crude product. This was recrystallized from benzene toremove syncarpic acid still present. Concentration of the mother liquorunder vacuum gave 1.7 g of the desired product as an oil, whichsolidified on standing (m.p. 76°-82° C.). It was identified as such bynuclear magnetic resonance spectroscopy, infrared spectroscopy and massspectroscopy.

The following are tables of certain selected compounds of EmbodimentsA-G' that are preparable according to the procedures described herein.Compound numbers are assigned to each compound and are used throughoutthe remainder of the application.

                                      TABLE I-A                                   __________________________________________________________________________     ##STR78##                                                                    Cmpd.                                         n.sub.D.sup.30 or               No. R         R.sup.1                                                                          R.sup.2                                                                           R.sup.3    R.sup.4  R.sup.5                                                                            m.p. °C.                 __________________________________________________________________________     1A CH.sub.3  CH.sub.3                                                                         Cl  H          H        H    1.5613                           2A CH.sub.3  CH.sub.3                                                                         Cl  H          4-Cl     H    1.5655                           3A CH.sub.3  CH.sub.3                                                                         Cl  H          H        6-Cl 103-108                          4A*                                                                              H         H  Cl  H          4-Cl     H    138-140                          5A CH.sub.3  CH.sub.3                                                                         Br  H          H        H                                     6A CH.sub.3  CH.sub.3                                                                         Cl  H          H        5-Cl 74-77                            7A H         H  Cl  H          H        5-Cl 104-107                          8A H         H  Br  H          H        H    93-96                            9A H         H  Cl  H          H        H    79-87                            10A                                                                              H         H  I   H          H        H    66-70                            11A                                                                              H         H  Cl  H          4-NO.sub.2                                                                             H    118-122                          12A                                                                              H         H  Cl  H          H        6-Cl 143-148                          13A                                                                              H         H  Cl  H          H        5-Br 109-115                          14A                                                                              H         H  I   3-I        H        5-I  164-167                          15A                                                                              H         H  Cl  H          H        5-CH.sub.3                                                                         60-65                            16A                                                                              H         H  Cl  H          4-CH.sub.3                                                                             H    79-86                            17A                                                                              H         H  Cl  H          4-CH.sub.3 O                                                                           H    60-63                            18A                                                                              H         H  Cl  3-Cl       H        6-Cl                                  19A                                                                              H         H  Cl  H          H        H    77-80                            20A                                                                              H         H  Cl  3-Cl       H        H    80-90                            21A                                                                              H         H  Cl  H          H        5-CF.sub.3                                                                         74-75                            22A                                                                              H         H  Cl  H          H        5-NO.sub.2                                                                         140-143                          23A                                                                              H         H  Cl  3-Cl       4-Cl     H    152-154                          24A                                                                              H         H  Cl  3-Cl       4-CH.sub.3 O                                                                           H    169-170                          25A                                                                              H         H  Cl  H          4-Br     H    104-107                          26A                                                                              CH.sub.3  CH.sub.3                                                                         CH.sub.3 O                                                                        H          H        H    104-108                          27A                                                                              H         H  Cl  H                                                                                         ##STR79##                                                                             H                                     28A                                                                              H         H  Br  H          H        .sup.(a)                              29A                                                                              H         H  CH.sub.3 O                                                                        3-CH.sub.3 O                                                                             H        H    75-79                            30A                                                                              H         H  CH.sub.3 O                                                                        H          H        5-CH.sub.3 O                                                                       89-92                            31A                                                                              H         H  Br  H          4-CH.sub.3 O                                                                           5-CH.sub.3 O                                                                       92-96                            32A                                                                              H         H  Br  H          (4) OCH.sub.2 O(5)                                                                          63-68                            33A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-Cl     H    86-89                            34A                                                                              H         H  Cl  3-Cl       H        5-Cl                                  35A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       H        5-Cl 105-109                          36A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-Cl     5-Cl 137-139                          37A                                                                              H         H  Cl  3-Cl       4-Cl     5-Cl 106-110                          38A                                                                              H         H  Cl  H          4-Cl     5-Cl 108-111                          39A                                                                               ##STR80##                                                                              H  Cl  H          4-Cl     H                                     40A                                                                               ##STR81##                                                                              H  Cl  H          4-Cl     H                                     41A                                                                              CH(CH.sub.3).sub.2                                                                      H  Cl  H          4-Cl     H                                     42A                                                                              CH(CH.sub.3).sub.2                                                                      H  Cl  3-Cl       4-Cl     H                                     43A                                                                              H         H  Cl  H          4-F      H                                     44A                                                                              sodium salt of Compound No. 23            85-94                            45A                                                                              isopropylamine salt of Compound No. 23    160-165                          46A                                                                              triethylamine salt of Compound No. 23     82-85                            47A                                                                              potassium salt of Compound No. 23         107-106                          48A                                                                              triethanolammonium salt of Compound No. 39                                 49A                                                                              sodium salt of Compound No. 43            60-63                            50A                                                                              CH(CH.sub.3).sub.2                                                                      H  Cl  3-CH.sub.3 O                                                                             4-Br     H                                     51A                                                                              H         H  Cl  H          4-CH.sub.3 SO.sub.2                                                                    H    140-141                          52A                                                                              H         CH.sub.3                                                                         Cl  H          4-Cl     H                                     53A                                                                              i-C.sub.4 H.sub.9                                                                       H  Cl  H          4-Cl     H                                     54A                                                                              i-C.sub.3 H.sub.7                                                                       H  Cl  3-CH.sub.3 O                                                                             H        H                                     55A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-CH.sub.3 SO.sub.2                                                                    H                                     56A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  3-CH.sub.3 4-Cl     H                                     57A                                                                              H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                            58A                                                                              H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H     98-102                          59A                                                                              H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.                                                              H     98-109                          60A                                                                              H         H  Cl  H          4-C.sub.3 H.sub.7 SO.sub.2                                                             H    semi-solid                       61A                                                                              H         H  Cl  3-CH.sub.3 O                                                                             4-CH.sub.3 SO.sub.2                                                                    H    48-59                            62A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    semi-solid                       63A                                                                              H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H      145-148.5                      64A                                                                              H         H  Cl  3-C.sub.2 H.sub.5 S                                                                      4-C.sub.2 H.sub.5 SO.sub.2                                                             H    oil                              65A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H    103-108                          66A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.2                                                             H    108-114                          67A                                                                              i-C.sub.3 H.sub.7                                                                       H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H    brown gum                        68A                                                                              H         H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                                                                    H    145-154                          69A                                                                              i-C.sub.3 H.sub.7                                                                       H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                                                                    H                                     70A                                                                              H         H  Br  H          4-CH.sub.3 SO.sub.2                                                                    H    brown gum                        71A                                                                              H         H  Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2                                                           H    semi-solid                       72A                                                                              H         H  Cl  H          4-CH.sub.3 S                                                                           H    74-77                            73A                                                                              H         H  Cl  3-Cl       4-CH.sub.3 S                                                                           H                                     74A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    120-123                          75A                                                                              H         H  Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2                                                           H    semi-solid                       76A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2                                                           H                                     77A                                                                              H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-CH.sub.3 SO.sub.2                                                                    H    semi-solid                       78A                                                                              H         H  Cl  3-CH.sub.3 O                                                                             4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    golden gum                       79A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2                                                           H    125-128                          80A                                                                              CH(CH.sub.3).sub.2                                                                      H  CH.sub.3 O                                                                        3-Cl       5-Cl     H                                     81A                                                                              HB        H  Cl  3-CH.sub.3 O                                                                             4-Br     H    101-111                          82A                                                                              H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                            83A                                                                              H         H  Cl  H          4-Cl     5-CH.sub.3 O                                                                       softens >70                      84A                                                                              CH(CH.sub.3).sub.2                                                                      H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-Br     H                                     85A                                                                              H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-Br     H    101-104                          86A                                                                              H         H  Cl  H          4-i-C.sub.4 H.sub.9 SO.sub.2                                                           H    136-140                          87A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2                                                           H                                     88A                                                                              H         H  Cl  3-Cl       4-i-C.sub.3 H.sub.7 SO.sub.2                                                           H    173-176                          89A                                                                              H         H  Cl  3-Cl       4-n-C.sub.4 H.sub.9 SO.sub.2                                                           H    135-138                          90A                                                                              H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-C.sub.2 H.sub.5 SO.sub.2                                                             H    gum                              91A                                                                              H         H  Cl  3-CH.sub.3 O                                                                             4-C.sub.2 H.sub.5 SO.sub.2                                                             H    gum                              92A                                                                              H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 S                                                                    H    91-94                            93A                                                                              H         H  Cl  3-C.sub.2 H.sub.5 S                                                                      4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    oil                              94A                                                                              H         H  Cl  3-C.sub.2 H.sub.5 S                                                                      4-C.sub.2 H.sub.5 S                                                                    H    oil                              95A                                                                              H         H  Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2                                                           H    oil                              96A                                                                              H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H                                     97A                                                                              H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H    oil                              98A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2                                                           H    oil                              99A                                                                              H         H  Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                    H    90-92                           100A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                    H                                    101A                                                                              H         H  Cl  H          4-C.sub.2 H.sub.5 S                                                                    H                                    102A                                                                              H         H  Cl  H          4-n-C.sub.3 H.sub.7 S                                                                  H                                    103A                                                                              H         H  Cl  H          4-i-C.sub.3 H.sub.7 S                                                                  H                                    104A                                                                              H         H  Cl  H          4-C.sub.2 H.sub.5 SO                                                                   H                                    105A                                                                              H         H  CH.sub.3 O                                                                        H          4-NO.sub.2                                                                             H    semi-solid                      106A                                                                              H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-Br     H                                    107A                                                                              H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-CH.sub.3 SO.sub.2                                                                    H     96-100                         108A                                                                              H         H  Cl  3-allyloxy 4-CH.sub.3 SO.sub.2                                                                    H    semi-solid                      109A                                                                              H         H  Cl  3-CH.sub.3 C(O)NH                                                                        4-Cl     H    155-160                         110A                                                                              H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 S                                                                  H                                    111A                                                                              H         H  Cl  3-CH.sub.3 O                                                                             4-NO.sub.2                                                                             H    150-153                         112A                                                                              H         H  Cl  3-allyloxy 4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    113A                                                                              H         H  Cl  3-CH.sub.2 BrCHBrCH.sub.2 O                                                              4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    114A                                                                              H         H  Cl  3-n-C.sub.4 H.sub.9 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H    gum                             115A                                                                              H         H  Cl  3-i-C.sub.4 H.sub.9 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    116A                                                                              H         H  Cl  H          4-allylthio                                                                            H                                    117A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-NO.sub.2                                                                             H                                    118A                                                                              H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                                                               4-Cl     H                                    119A                                                                              H         H  Cl  3-i-C.sub.3 H.sub.7 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    120A                                                                              H         H  Cl  3-CH.sub.2 ClCH.sub.2 CH.sub.2 O                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                             H    gum                             121A                                                                              H         H  Cl  H          4-t-C.sub.4 H.sub.9 S                                                                  H                                    122A                                                                              H         H  Cl  3-CH.sub.3 O                                                                             4-C.sub.2 H.sub.5 S                                                                    H                                    123A                                                                              H         H  Cl  H          4-CF.sub.3                                                                             H                                    124A                                                                              H         H  Cl  H          4-Cl     6-Cl                                 124A                                                                              H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                                                               H        H    131-135                         126A                                                                              H         H  Cl  3-CH.sub.3 C(O)NH                                                                        H        H                                    127A                                                                              H         H  Cl  3-(CH.sub.3).sub.2 N                                                                     4-Cl     H                                    128A                                                                              CH.sub.3  H  Cl  3-CH.sub.3 O                                                                             4-CH.sub.3 SO.sub.2                                                                    H    117-122                         129A                                                                              H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    130A                                                                              H         H  Br  H          H        H                                    131A                                                                              H         H  Br  H          4-C.sub.2 H.sub.5 OC(O)                                                                H                                    132A                                                                              H         H  Cl  H          4-CN     H    183-184                         133A                                                                              H         H  Cl  3-CH.sub.3 C(O)NH                                                                        H        6-NO.sub.2                           134A                                                                              H         H  Cl  3-(CH.sub.3).sub.2 N                                                                     H        H                                    135A                                                                              H         H  Cl  3-Cl       4-ClCH.sub.2 CH.sub.2 SO.sub.2                                                         H                                    __________________________________________________________________________     * = prepared in Example 1A.                                                   ##STR82##                                                                

                                      TABLE I-B                                   __________________________________________________________________________     ##STR83##                                                                    Compound                                                                      Number                                                                              R.sup.10 R.sup.11                                                                          R.sup.12                                                                          R.sup.13                                                                            R.sup.14  R.sup.15                                                                         R.sup.16                                                                         R.sup.17                                                                         R.sup.18                      __________________________________________________________________________     1B                                                                                  ##STR84##                                                                             H   Cl  H     4-Cl      H  H  H  H                              2B                                                                                  ##STR85##                                                                             CH.sub.3                                                                          Cl  H     4-Cl      H  H  H  H                              3B   triethanolammonium salt of Compound No. 2                                4B   triethanolammonium salt of Compound No. 7                                5B                                                                                  ##STR86##                                                                             CH.sub.3                                                                          Cl  3-Cl  4-Cl      H  H  H  H                              6B   triethanolammonium salt of Compound No. 5                               .sup. CH.sub.3a                                                                              CH.sub.3                                                                          Cl  H     4-Cl      H  H  H  H                              8B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                              9B   CH.sub.3 n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl      H  H  H  H                             10B   CH.sub.3 H   Cl  H     4-Cl      H  H  H  H                             11B   CH.sub.3 H   Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             12B   C.sub.5 H.sub.10                                                                           Cl  H     4-Cl      H  H  H  H                             13B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-Cl      H  H  H  H                             14B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H                             15B   i-C.sub.3 H.sub.7                                                                      H   Cl  3-Cl  4-Cl      H  H  H  H                             16B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             17B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             18B   CH.sub.3 H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             19B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             20B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             21B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             22B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             23B   CH.sub.3 CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             24B   CH.sub.3 CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             25B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             26B   CH.sub.3 CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             27B   CH.sub.3 C.sub.2 H.sub.5                                                                   Cl  H     4-Cl      H  H  H  H                             28B   CH.sub.3 CH.sub.3                                                                          Cl  H     H         H  H  H  H                             29B   CH.sub. 3                                                                              CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-Br      H  H  H  H                             30B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Br      H  H  H  H                             31B   CH.sub.3 C.sub.2 H.sub.5                                                                   Cl  3-Cl  4-Cl      H  H  H  H                             32B   n-C.sub.3 H.sub.7                                                                      H   Cl  H     4-Cl      H  H  H  H                             33B                                                                                  ##STR87##                                                                             n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl      H  H  H  H                             34B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             35B   CH.sub.3 CH.sub.3                                                                          Cl  3-i-C.sub.3 H.sub.7 O                                                               4-Br      H  H  H  H                             36B   CH.sub.3 CH.sub.3                                                                          Cl  H     6-F       H  H  H  H                             37B   i-C.sub.3 H.sub.7                                                                      H   Cl  3-Cl  4-Cl      H  H  H  H                             38B   CH.sub.3 CH.sub.3                                                                          Cl  3-OC.sub.2 H.sub.5                                                                  4-Br      CH.sub.3                                                                         H  H  H                             39B   i-C.sub.3 H.sub.7 OC(O)                                                                H   Cl  H     4-Cl      H  H  H  H                             40B   C.sub.2 H.sub.5 OC(O)                                                                  n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl      H  H  H  H                             41B   C.sub.5 H.sub.10                                                                           Cl  H     4-Cl      H   H H  H                             42B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Cl      H  H  CH.sub.3                                                                         H                             43B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             44B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             45B   CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        3-CH.sub.3 O                                                                        H         H  H  H  H                             46B   CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     4-Cl      H  H  H  H                             47B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Br      CH.sub.3                                                                         H  H  H                             48B   CH.sub.3 CH.sub.3                                                                          Br  H     H         H  H  H  H                             49B   CH.sub.3 CH.sub.3                                                                          I   H     H         H  H  H  H                             50B   CH.sub.3 CH.sub.3                                                                          F   H     H         H  H  H  H                             51B   CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     H         H  H  H  H                             52B   CH.sub.3 CH.sub.3                                                                          Cl  3-allyloxy                                                                          4-Br      H  H  H  H                             53B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  CH.sub.3                                                                         H                             54B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        4-Br      CH.sub.3                                                                         H  H  H                             55B   CH.sub. 3                                                                              CH.sub.3                                                                          Br  H     4-CN      H  H  H  H                             56B   CH.sub.3 CH.sub.3                                                                          Cl  H     4N(CH.sub.3)SO.sub.2 CF.sub.3                                                           H  H  H  H                             57B   CH.sub.3 CH.sub.3                                                                          Cl  3-NO.sub.2                                                                          H         H  H  H  H                             58B   CH.sub.3 CH.sub.3                                                                          C.sub.2 H.sub.5 O                                                                 H     4-Cl      H  H  H  H                             59B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             60B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             61B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             62B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             63B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                                                            CH.sub.3                                                                         H  H  H                             64B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             65B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-F       H  H  H  H                             66B   CH.sub.3 H   Cl  3-CH.sub.3 O                                                                        4-Br      H  H  H  H                             67B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        H         H  H  H  H                             68B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             69B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             70B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             71B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             72B   CH.sub.3 CH.sub.3                                                                          Cl  Cl    4-i-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             73B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             74B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             75B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-Br      H  H  H  H                             76B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             77B   CH.sub.3 CH.sub.3                                                                          Cl  3-n-C.sub.3 H.sub.7 O                                                               4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             78B   CH.sub. 3                                                                              CH.sub.3                                                                          Cl  H     4-(CH.sub.3).sub.2 NHO.sub.2                                                            H  H  H  H                             79B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 S                                                                        4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             80B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-C.sub.2 H.sub.5 S                                                                     H  H  H  H -81B CH.sub.3 CH.sub.3 C                                                    l H 4-C.sub.2 H.sub.5                                                         S H H H H                     82B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                     H  H  H  H                             83B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             84B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 S                                                                   CH.sub.3                                                                         H  H  H                             85B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 S(O)                                                                  H  H  H  H                             86B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.3 H.sub.7 S                                                                   H  H  H  H                             87B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.3 H.sub.7 S                                                                   H  H  H  H                             88B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-t-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             89B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.3 H.sub.7 S                                                                   CH.sub.3                                                                         H  H  H                             90B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                            CH.sub.3                                                                         H  H  H                             91B   CH.sub.3 CH.sub.3                                                                          Cl  *     4-Cl      H  H  H  H                             92B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.2CHCH.sub.2 S                                                                  H  H  H  H                             93B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             94B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-CH.sub.3 S                                                                            CH.sub.3                                                                         H  H  H                             95B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 S                                                                            H  H  H  H                             96B   CH.sub.3 CH.sub.3                                                                          Cl  3-i-C.sub.3 H.sub.7 O                                                               4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             97B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             98B   CH.sub.3 CH.sub.3                                                                          Cl  **    4-Cl      H  H  H  H                             99B   CH.sub.3 CH.sub.3                                                                          Cl  **    H         H  H  H  H                             100B  CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-CH.sub.3 S                                                                            H  H  H  H                             101B  CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     4-NO.sub.2                                                                              H  H  H  H                             102B  CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     4-CF.sub.3                                                                              H  H  H  H                             103B  CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO                                                                  H  H  H  H                             104B  CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO                                                                  CH.sub.3                                                                         H  H  H                             __________________________________________________________________________    The following additional compounds can be prepared by the                     general method hereinbefore taught.                                           CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  H     4-Cl      H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  H     4-Cl      H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  H     4-Cl      H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  H     4-Cl      H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-Cl      H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-Cl      H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-Cl  4-Cl      H  H  H  H                             CH.sub.3       H   Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-Cl  4-Cl      H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  4-Cl  H         H  H  H                                n-C.sub.4 H.sub.9                                                                            H   Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H -                           C.sub.5 H.sub.10   Cl  3-Cl  4-Cl      H  H  H                                C.sub.5 H.sub.10   Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H                                CH.sub. 3      n-C.sub.3 H.sub.7                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H                                C.sub.5 H.sub.10   Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             C.sub.5 H.sub.10   Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3        n-C.sub.3 H.sub.7                                                                Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             C.sub.5 H.sub.10   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.5 H.sub.10   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       H   Cl  H     4-C.sub. 2 H.sub.5 SO.sub.2                                                             CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.5 H.sub.10   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.5 H.sub.10   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             CH.sub.3       H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             C.sub.5 H.sub.10   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10    Cl 3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             C.sub.5 H.sub.10   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             CH.sub.3       H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                        H  H  H                             C.sub.5 H.sub.10   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             CH.sub.3       H   Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             C.sub.5 H.sub.10   Cl  3-CH.sub.3                                                                          4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             CH.sub.3       n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             CH.sub.3       n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       H   Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             CH.sub.3       H   Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             C.sub.2 H.sub.5                                                                              H   Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             n-C.sub.4 H.sub.9                                                                            H   Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             i-C.sub.3 H.sub.7                                                                            H   Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             C.sub.5 H.sub.10   Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             C.sub.5 H.sub.10   Cl  3-OCH.sub.3                                                                         4-Cl      CH.sub.3                                                                         H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-n-C.sub.3 H.sub.7 O                                                               4-Br      H  H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             CH.sub. 3      CH.sub.3                                                                          Cl  H     4-NO.sub.2                                                                              H  H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-CH.sub.3 S                                                                            H  H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  H     4-CN      H  H  H  H                             CH.sub.3       CH.sub.3                                                                          Cl  3-(CH.sub.3).sub.2 N                                                                4-Cl      H  H  H  H                             __________________________________________________________________________     .sup.a Prepared in Example IB.                                                *= 3-CH.sub.3 C(O)NH                                                          **= 3-CH.sub.3 C(O)N(CH.sub.3)                                           

                  TABLE I-C                                                       ______________________________________                                         ##STR88##                                                                    Comp.                                                                         No.   R.sup.21                                                                             R.sup.22                                                                             R.sup.23 R.sup.24 R.sup.25                                                             R.sup.26 R.sup.27                                                                    R.sup.28                                                                           n.sub.D.sup.30 or                    ______________________________________                                                                                 m.p.                                 .sup.1 1C.sup.(a)                                                                   CH.sub.3                                                                             CH.sub.3                                                                             HHH      HH     H    oil                                  2C    H      H      HHH      HH     CN   124-140° C.                   ______________________________________                                         .sup.(a) Prepared in Example IC.                                         

                                      TABLE I-D                                   __________________________________________________________________________     ##STR89##                                                                    Comp.                                                                         No. R.sup.31                                                                         R.sup.32                                                                          R.sup.33                                                                          R.sup.34                                                                         R .sup.35                                                                        R.sup.36                                                                         R.sup.37                                                                           R.sup.38 n.sub.D.sup.30 or                       __________________________________________________________________________                                          m.p.                                     1D CH.sub.3                                                                         H   H   H  H  H  H    H        viscous oil                              2D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    H        viscous oil                              3D.sup.(a)                                                                       H  H   H   H  H  H  H    H        132-135                                  4D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    H        viscous oil                              5D.sup.(b)                                                                       H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    H        130-133                                  6D CH.sub.3                                                                         H   H   H  CH.sub.3                                                                         H  H    H        viscous oil                              7D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    CF.sub.3 52-61                                    8D H  H   H   H  H  H  H    CF.sub.3 88-94                                    9D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    CF.sub.3 89-97                                   10D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-CH.sub.3                                                                         H        119-122                                 11D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-Cl H        72-79                                   12D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    Cl       118-121                                 13D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-Cl H        118-120                                 14D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-F  H        130-133                                 15D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-CH.sub.3 O                                                                       H        139-142                                 16D CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                          H  H  H  H    CF.sub.3 viscous oil                             17D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    NO.sub.2 viscous oil                             18D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    Br       viscous oil                             19D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  CH.sub.3                                                                         5-CH.sub.3                                                                         H        viscous oil                             20D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-CH.sub. 3                                                                        H        viscous oil                             21D H  H   H   H  H  H  H    F        123-128                                 22D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    F        viscous oil                             23D H  H   H   H  H  H  H    Cl       viscous oil                             24D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 CH.sub.3                                                                      130-133                                 25D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2n-C.sub.3 H.sub.7                                                              viscous oil                             26D H  H   H   H  H  H  H    SO.sub.2 CH.sub.3                                                                      157-159                                 27D H  H   H   H  H  H  H    SO.sub.2n-C.sub.3 H.sub.7                                                              120-123                                 28D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-F  H        165-195                                 29D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                                                                oil                                     30D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    SO.sub.2CH.sub.3                                                                       gum                                     31D CH.sub.3                                                                         n-C.sub.4 H.sub.9                                                                 H   H  H  H  H    H        viscous oil                             32D H  H   i-C.sub.4 H.sub.9                                                                 H  H  H  H    H        viscous oil                             33D H  H   H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                                                                viscous oil                             34D H  H   H   H  H  H  H    CN       viscous oil                             35D H  H   H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                                                             158-159                                 36D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                                                             120-130                                 37D H  H   H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                      158-163                                 38D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                      oil                                     39D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H                                                                                   ##STR90##                                                                             oil                                     40D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    SO.sub.2N(C.sub.2 H.sub.5).sub.2                                                       oil                                     41D H  H   H   H  H  H  H    SC.sub.2 H.sub.5                                                                       oil                                     42D H  H   H   H  H  H  H    S(O)n-C.sub.3 H.sub.7                                                                  oil                                     43D H  H   H   H  H  H  H    Sn-C.sub.3 H.sub.7                                                                     oil                                     44D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    Sn-C.sub.3 H.sub.7                                                                     oil                                     45D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    Sn-C.sub.3 H.sub.7                                                                     oil                                     46D CH.sub.3                                                                         CH.sub. 3                                                                         H   H  CH.sub.3                                                                         H  H    SC.sub.2 H.sub.5                                                                       oil                                     47D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SC.sub.2 H.sub.5                                                                       oil                                     47D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SC.sub.2 H.sub.5                                                                       oil                                     48D H  H   H   H  H  H  H    SCH.sub.3                                                                              94-97                                   49D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    CF.sub.3 oil                                     50D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SCH.sub.3                                                                              oil                                     51D .sup.(c)                                                                         H   i-C.sub.3 H.sub.7                                                                 H  H  H  H    H        145-148                                 52D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-CH.sub.3 O                                                                       Br       oil                                     53D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    Cl       oil                                     54D H  H   H   H  H  H  3-CH.sub.3 O                                                                       Cl       oil                                     55D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-CH.sub.3 O                                                                       Cl       oil                                     56D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    CH.sub.3 S                                                                             oil                                     57D H  H   H   H  H  H  H                                                                                   ##STR91##                                                                             120-125                                 58D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    CN       175-177                                 59D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    CN       151-153                                 60D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    CN       oil                                     61D .sup.(c)                                                                         H   H   H  H  H  H    H        oil                                     62D .sup.(d)                                                                         H   H   H  H  H  H    H        oil                                     63D H  H   CH.sub.3                                                                          H  H  H  H    Cl       110-115                                 64D H  H   CH.sub.3                                                                          H  H  H  H    SO.sub.2n-C.sub.3 H.sub.7                                                              oil                                     65D .sup.(d)                                                                         CH.sub.3                                                                          H   H  H  H  H    Cl       oil                                     66D H  H   H   H  H  H  H    SO.sub.2 CHCl.sub.2                                                                    oil                                     67D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 CHCl.sub.2                                                                    oil                                     68D H  H   H   H  H  H  .sup.(c)                                                                           Br       oil                                     69D H  H   H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                                                                   oil                                     70D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                                                                   wax                                     71D .sup.(d)                                                                         CH.sub.3                                                                          H   H  H  H  H    H        oil                                     72D H  H   H   H  H  H  C.sub.2 H.sub.5 O                                                                  Cl       oil                                     73D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  CH.sub.3 O                                                                         CF.sub.3 oil                                     __________________________________________________________________________     .sup.(a) Prepared in Example 1D,D'.                                           .sup.(b) Prepared in Example 2D,D'.                                           .sup.(c) = C.sub.2 H.sub.5 OC(O)-                                             .sup.(d) = iC.sub.3 H.sub.7 OC(O)-                                       

                                      TABLE I-E                                   __________________________________________________________________________     ##STR92##                                                                    Comp.                                                                         No. n R.sup.40                                                                         R.sup.41                                                                         R.sup.42                                                                         R.sup.43                                                                         R.sup.44                                                                         R.sup.45                                                                         R.sup.46                                                                         R.sup.47                                                                          R.sup.48                                                                             m.p.                                    __________________________________________________________________________     1E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   H      79-81° C.                         2E 0 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   H      oil                                     .sup.  3E.sup.a                                                                   0 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  CH.sub.3                                                                         H  H   H      oil                                     .sup.  4E.sup.b                                                                   2 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  CH.sub.3                                                                         H  H   H      oil                                      5E 0 C.sub.2 H.sub.5                                                                  CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   H      oil                                      6E 2 C.sub.2 H.sub.5                                                                  CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   H      oil                                      7E 0 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              Cl     59-64° C.                         8E 2 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              Cl     116-119° C.                       9E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   CF.sub.3                                                                             102-106° C.                      10E 2 CH.sub.3                                                                         H  H  H  H  H  H  H   CF.sub.3                                                                             oil                                     11E 0 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   CF.sub.3                                                                             49-53° C.                        12E 2 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   CF.sub.3                                                                             oil                                     .sup. 13E.sup.c                                                                   1 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   CF.sub.3                                                                             oil                                     14E 0 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              SCH.sub.3                                                                            105-107° C.                      15E 1 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              S(O)CH.sub.3                                                                         oil                                     16E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                                                           oil                                     17E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   SCH.sub.3                                                                            101-103° C.                      18E 2 CH.sub.3                                                                         H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                                                           oil                                     19E 2 CH.sub.3                                                                         H  H  H  H  H  H  H   SO.sub.2 CH.sub.3                                                                    194-196° C.                      20E 0 CH.sub.3                                                                         H  H  H  H  H  H  3-CH.sub.3                                                                        H      40-42° C.                        21E 2 CH.sub.3                                                                         H  H  H  H  H  H  3-CH.sub.3                                                                        H      80-86° C.                        __________________________________________________________________________     .sup.a Prepared in Example 1E,E'.                                             .sup.b Prepared in Example 2E,E'.                                             .sup.c Prepared in Example 3E,E'.                                        

                                      TABLE I-F                                   __________________________________________________________________________     ##STR93##                                                                    Comp.                                 n.sub.D.sup.30                          No. R.sup.50                                                                         R.sup.51                                                                         R.sup.52                                                                         R.sup.53                                                                          R.sup.54                                                                         R.sup.55                                                                         R.sup.56                                                                         R.sup.57                                                                          R.sup.58                                                                              or m.p.                                 __________________________________________________________________________     1F CH.sub.3                                                                         H  H  H   H  H  H  H   H       35-42° C.                         2F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   H       47-53° C.                         3F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Br      oil                                      4F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CN      oil                                      5F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-NO.sub.2                                                                        H       oil                                      6F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  5-Cl                                                                              H       oil                                      7F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CH.sub.3 SO.sub.2                                                                     oil                                      8F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CH.sub.3 SO.sub.2                                                                     oil                                      9F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-Cl                                                                              H       oil                                     10F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     11F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     12F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                                                            oil                                     13F CH.sub.3                                                                         H  H  H   H  H  H  H   CH.sub.3 SO.sub.2                                                                     oil                                     14F CH.sub.3                                                                         H  H  H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                                                            oil                                     15F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CH.sub.3 S                                                                            oil                                     16F C.sub.2 H.sub.5                                                                  CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Br      oil                                     17F CH.sub.3                                                                         H  H  H   H  H  H  H   CN      oil                                     18F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   F       oil                                     19F CH.sub.3                                                                         H  H  H   H  H  H  H   C.sub.2 H.sub.5SO.sub.2                                                               oil                                     20F CH.sub.3                                                                         H  H  H   H  H  H  3-Cl                                                                              H       65-67° C.                        21F CH.sub.3                                                                         H  H  H   H  H  H  3-I H       oil                                     22F CH.sub.3                                                                         H  H  H   H  H  H  3-NO.sub.2                                                                        H       oil                                     23F CH.sub.3                                                                         H  H  H   H  H  H  3-CN                                                                              H        96-101° C.                      24F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   H       oil                                     25F CF.sub.3                                                                         H  H  H   H  H  H  H   H       oil                                     26F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Br      oil                                     27F CF.sub.3                                                                         H  H  H   H  H  H  H   Cl      82-88° C.                        28F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Cl      oil                                     29F CF.sub.3                                                                         H  H  H   H  H  H  H   C.sub.2 H.sub.5 S                                                                     oil                                     30F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   C.sub.2 H.sub.5 SO.sub. 2                                                             oil                                     31F CF.sub.3                                                                         H  H  H   H  H  H  H   CN      oil                                     32F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CN      oil                                     .sup. 33F.sup.a                                                                   CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   Br      oil                                     34F CH.sub.3                                                                         H  H  H   H  H  H  H   CH.sub.3                                        35F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-Cl                                                                              C.sub.2 H.sub.5 SO.sub.2                                                              115-117° C.                      36F CH.sub.3                                                                         H  H  H   H  H  H  3-Cl                                                                              C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     37F CH.sub.3                                                                         .sup.b                                                                           .sup.b                                                                           H   H  H  H  3-CF.sub.3                                                                        H       oil                                     38F CH.sub.3                                                                         .sup.c                                                                           H  i-C.sub.3 H.sub.7                                                                 H  H  H  3-NO.sub.2                                                                        H        88-108° C.                      39F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CH.sub.3 S                                                                            oil                                     40F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CH.sub.3 S                                                                            oil                                     41F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CH.sub.3 SO.sub.2                                                                     oil                                     42F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CF.sub.3                                                                              oil                                     43F CH.sub.3                                                                         H  H  H   H  H  H  H   CF.sub.3                                                                              114-120° C.                      44F CH.sub.3                                                                         H  H  H   H  H  H  3-Cl                                                                              Cl      oil                                     45F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-Cl                                                                              Cl      oil                                     46F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-CF.sub.3                                                                        H       oil                                     47F CF.sub.3                                                                         H  H  H   H  H  H  H   CH.sub.3 S                                                                            oil                                     48F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CF.sub.3                                                                              oil                                     49F CF.sub.3                                                                         H  H  H   H  H  H  H   CF.sub.3                                                                              oil                                     50F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CF.sub.3                                                                              oil                                     51F CH.sub.3                                                                         H  H  CH.sub.3                                                                          H  H  H  H   CH.sub.3 SO.sub.2                                                                     oil                                     52F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     53F CH.sub.3                                                                         H  H  H   H  H  H  H   Br      94-98° C.                        54F CH.sub.3                                                                         H  H  H   H  H  H  .sup.d                                                                            H       oil                                     __________________________________________________________________________     .sup.a Prepared in Example 1F,F'.                                             .sup.b (CH.sub.2).sub.5                                                       .sup.c C.sub.2 H.sub.5 OC(O)-                                                 .sup.d 3-N(CH.sub.3)COCH.sub.3                                           

                                      TABLE I-G                                   __________________________________________________________________________     ##STR94##                                                                    Comp.                                                                         No. R.sup.60                                                                           R.sup.61                                                                         R.sup.62                                                                         R.sup.63                                                                         R.sup.64                                                                         R.sup.65                                                                           R.sup.66                                                                              m.p. °C.                             __________________________________________________________________________     1G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    H       112-117                                     .sup.  2G.sup.a                                                                   NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-Cl    76-82                                        3G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 CH.sub.3                                                                   .sup. 176-179°                        4G CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 C.sub.2 H.sub.5                                                            gum                                          5G CF.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CF.sub.3                                                                            viscous oil                                  6G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 CH.sub.2 Cl                                                                oil                                          7G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-F     gum                                          8G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-OC.sub.2 H.sub.5                                                                 4-SO.sub.2 C.sub.2 H.sub.5                                                            gum                                          9G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 CH.sub.3                                                                   gum                                         10G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SCH.sub.3                                                                           gum                                         11G CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-NO.sub.2                                                                         H       gum                                         12G I    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    H       gum                                         13G OCH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-Cl    gum                                         14G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-OCH.sub.3                                                                        4-Br    gum                                         15G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 nC.sub.3 H.sub.7                                                           gum                                         16G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 N(CH.sub.3).sub.2                                                          gum                                         17G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CN    .sup.  148-150°                      18G SO.sub.2 CH.sub.3                                                                  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    H       gum                                         19G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CF.sub.3                                                                            gum                                         20G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-Cl    gum                                         21G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SCF.sub.3                                                                           gum                                         22G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-OCF.sub.3                                                                           gum                                         23G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                            gum                                         24G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-C(O)CH.sub.3                                                                        gum                                         25G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2CH.sub.3                                                                    129-131                                     26G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SCH.sub.3                                                                           89-92                                       27G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CF.sub.3                                                                            115-125                                     28G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CN    87-95                                       __________________________________________________________________________     .sup.a prepared in Example 1G,G'.                                        

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in theabove-described manner are phytotoxic compounds which are useful andvaluable in controlling various plant species. Selected compounds ofthis invention were tested as herbicides in the following manner.

Pre-emergence herbicide test

On the day preceding treatment, seeds of eight different weed speciesare planted in loamy sand soil in individual rows using one species perrow across the width of a flat. The seeds used are green foxtail (FT)(Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat(WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa),velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassicajuncea), redroot pigweed (PW) (Amaranthus retroflexus) or curly dock(CD) (Rumex crispus), and yellow nutsedge (YNG) (Cyperus esculentus).Ample seeds are planted to give about 20 to 40 seedlings per row, afteremergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to betested are weighed out on a piece of glassine weighing paper. The paperand compound are placed in a 60 milliliter (ml) wide-mouth clear bottleand dissolved in 45 ml of acetone or substituted solvent. Eighteen ml ofthis solution are transferred to a 60 ml wide-mouth clear bottle anddiluted with 22 ml of a water and acetone mixture (19:1) containingenough polyoxyethylene sorbitan monolaurate emulsifier to give a finalsolution of 0.5% (v/v). The solution is then sprayed on a seeded flat ona linear spray table calibrated to deliver 80 gallons per acre (748L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperatureof 70° to 80° F. and watered by sprinkling. Two weeks after treatment,the degree of injury or control is determined by comparison withuntreated check plants of the same age. The injury rating from 0 to 100%is recorded for each species as percent control with 0% representing noinjury and 100% representing complete control.

The results of the tests are shown in the following Tables:

                                      TABLE II-A                                  __________________________________________________________________________    Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 __________________________________________________________________________    Cmpd. No.                                                                           FT  WG WO AMG VL  MD PW CD YNG                                          __________________________________________________________________________     1A   100 90 20 40  65  50 35    80                                            2A   80  90 0  30  80  90 20    90                                            3A   0   0  0  40  40  40 0     0                                             4A   100 100                                                                              50 35  100 100                                                                              90    95                                            5A   100 95 65 35  90  85 50    95                                            6A   50  25 0  25  100 100                                                                              35    80                                            7A   80  90 10 60  100 100                                                                              100   80                                            8A   95  95 45 40  100 80 95    95                                            9A   95  100                                                                              55 30  100 90 100   95                                           10A   100 100                                                                              60 20  85  100                                                                              100   95                                           11A   85  100                                                                              30 40  100 100                                                                              100   95                                           12A   85  85 90 75  80  95 90    90                                           13A   85  75 10 10  85  65 95    90                                           14A   40  10 80 0   65  40 65    100                                          15A   40  60 20 30  100 30 75    95                                           16A   80  80 20 55  75  90 40    95                                           17A   20  -- 10 25  100 95 85    90                                           18A   65  -- 30 70  100 100                                                                              85    90                                           19A   45  60 0  30  40  0  20    60                                           20A   30  85 20 40  95  85 40    45                                           21A   80  100                                                                              0  80  100 100                                                                              95    95                                           22A   20  10 0  20  75  30 45    10                                           23A   45  95 10 0   100 85 100   95                                           24A   --  100                                                                              0  25  70  90 --    100                                          25A   --  100                                                                              25 80  100 100                                                                              --    100                                          26A   40  15 0  0   0   10    0  30                                           27A   40  80 10 20  60  50    30 75                                           28A   65  75 0  65  100 95    75 55                                           29A   100 95 55 10  80  75    85 95                                           30A   20  20 20 10  40  40    50 20                                           31A   75  95 20 20  100 95    75 10                                           32A   90  85 20 0   100 85    75 30                                           33A   80  70 0  40  20  40    90 80                                           34A   60  40 0  20  95  100   100                                                                              60                                           35A   0   10 0  0   10  20    20 10                                           36A   0   0  0  20  100 100   100                                                                              0                                            37A   40  0  0  20  100 60    90 --                                           38A   10  40 0  20  90  80    20 20                                           39A   80  10 0  0   0   0     0  90                                           40A   60  0  0  0   0   0     0  90                                           41A   100 100                                                                              85 40  95  100   100                                                                              100                                          42A   60  100                                                                              25 0   0   0     0  25                                           43A   100 100                                                                              45 40  80  90    90 100                                          44A   90  100                                                                              0  60  100 100   100                                                                              95                                           45A   100 100                                                                              0  60  100 100   100                                                                              100                                          46A   20  60 0  100 100 100   100                                                                              20                                           47A   60  70 20 100 100 100   100                                                                              60                                           48A   60  0  0  0   0   0     0  40                                           49A   100 100                                                                              50 10  60  20    90 100                                          50A   100 100                                                                              80 10  60  60    90 100                                          51A   100 100                                                                              90 100 100 100   85 100                                          52A   100 100                                                                              60 10  100 100   60 100                                          53A   0   20 0  0   20  20    0  10                                           54A   10  45 10 0   0   0     0  40                                           55A   90  100                                                                              60 100 100 100   90 100                                          56A   40  70 40 40  40  60    70 50                                           57A   100 100                                                                              90 100 100 100   85 100                                          58A   90  95 0  20  20  40    40 100                                          59A   95  100                                                                              85 75  100 100   90 98                                           60A   95  100                                                                              50 50  100 100   90 98                                           61A   100 100                                                                              75 100 100 100   95 95                                           62A   100 100                                                                              95 75  100 100   100                                                                              80                                           63A   100 100                                                                              40 65  100 100   100                                                                              95                                           64A   100 100                                                                              98 100 100 100   100                                                                              90                                           65A   100 100                                                                              80 100 100 100   100                                                                              90                                           66A   100 100                                                                              75 100 100 100   100                                                                              98                                           73A   100 100                                                                              60 80  100 100   75 90                                           74A   100 100                                                                              70 80  100 100   80 100                                          75A   70  100                                                                              0  50  100 100   100                                                                              80                                           76A   40  90 25 10  100 100   100                                                                              10                                           77A   100 100                                                                              90 100 100 100   85 --                                           78A   100 100                                                                              80 100 100 100   90 --                                           79A   50  100                                                                              50 50  95  100   100                                                                              60                                           80A   0   0  0  0   0   0     0  0                                            81A   100 100                                                                              50 15  100 100   90 100                                          84A   100 100                                                                              85 0   0   100   20 100                                          88A   60  95 35 95  100 100   95 80                                           89A   75  100                                                                              40 100 100 100   95 60                                           90A   100 100                                                                              90 100 100 100   100                                                                              85                                           105A  80  95 25 0   95  50    70 50                                           __________________________________________________________________________    Cmpd. No.                                                                           FT  WG WO AMG VL  MD PW CD YNS                                          __________________________________________________________________________    117A  95  100                                                                              0  25  100 100   50 95                                           118A  100 100                                                                              60 100 100 100   100                                                                              85                                           121A  95  100                                                                              50 75  100 95    100                                                                              80                                           125A  100 100                                                                              50 80  100 100   100                                                                              85                                           126A  70  100                                                                              80 80  100 100   100                                                                              80                                           127A  100 100                                                                              100                                                                              100 100 100   -- 80                                           128A  100 100                                                                              100                                                                              100 100 100   -- 80                                           129A  100 100                                                                              95 90  100 100   -- 80                                           131A  70  85 0  20  95  98    95 90                                           132A  100 100                                                                              95 90  100 100   -- 80                                           133A  100 100                                                                              100                                                                              100 100 100   -- 80                                           135A  100 100                                                                              100                                                                              80  100 100   -- 80                                           __________________________________________________________________________

                  TABLE II-B                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG   VL    MD   CD   YNS                            ______________________________________                                         1B   0      85     10   75    100   80   80   75                              2B   90     100    65   100   100   100  100  100                             4B   100    100    80   60    100   80   90   100                             5B   80     100    20   40    100   100  80   100                             6B   40     100    0    40    100   100  80   100                             7B   100    100    100  80    100   100  90   100                             8B   100    100    60   45    60    60   80   100                             9B   60     100    40   20    60    60   60   100                            10B   100    100    40   5     80    60   80   100                            11B   100    100    90   10    20    20   40   100                            12B   0      20     0    0     10    20   10   0                              13B   100    100    90   40    100   100  100  100                            15B   90     90     50   20    --    100  100  80                             16B   100    100    95   100   100   100  90   100                            17B   100    100    100  100   100   100  100  97                             18B   100    100    85   100   100   100  90   95                             19B   100    100    95   100   100   100  100  95                             20B   100    100    85   100   100   100  100  90                             21B   100    100    100  100   100   100  100  95                             22B   100    100    80   100   100   100  100  90                             25B   100    100    75   80    100   100  100  90                             26B   100    100    65   30    100   100  100  90                             27B   20     95     60   5     100   100  90   100                            28B   100    100    80   20    90    40   80   100                            29B   100    100    70   20    100   100  100  100                            30B   100    100    80   60    100   100  80   100                            31B   80     100    40   10    60    60   80   100                            32B   20     40     10   0     --    60   100  60                             33B   0      10     0    0     10    10   0    0                              34B   100    100    90   80    100   100  90   100                            35B   100    100    90   40    90    90   90   90                             36B   100    100    85   0     95    85   95   90                             37B   90     90     50   20    --    100  100  80                             39B   15     100    0    50    100   80   70   40                             40B   0      10     0    0     10    10   0    0                              41B   0      20     0    0     10    20   10   0                              42B   100    100    90   45    100   100  65   100                            43B   100    100    90   100   100   100  100  90                             44B   100    100    85   100   100   100  100  95                             45B   65     100    0    0     100   20   20   90                             46B   100    100    0    20    100   100  98   85                             47B   100    100    90   85    100   100  100  95                             48B   100    100    85   15    100   100  85   95                             49B   100    100    65   0     100   100  50   50                             50B   80     80     55   0     98    55   80   65                             51B   95     95     10   0     65    0    25   60                             52B   100    100    100  100   100   100  100  50                             53B   100    100    75   100   100   100  100  50                             54B   100    100    60   15    100   100  100  80                             55B   100    100    55   15    100   100  90   95                             56B   100    100    60   20    95    100  90   10                             57B   5      10     0    0     40    20   0    0                              58B   10     40     10   10    95    40   100  80                             59B   100    100    75   80    100   100  100  75                             60B   100    100    90   100   100   100  85   --                             61B   100    100    80   100   100   100  100  --                             62B   95     100    50   95    100   100  85   --                             63B   100    100    70   100   90    100  100  --                             64B   100    100    75   100   100   100  85   --                             65B   100    100    55   40    100   100  90   70                             66B   100    100    65   35    100   100  100  95                             67B   100    100    30   15    100   100  95   90                             71B   100    100    80   100   100   100  80   --                             72B   100    100    40   100   100   100  90   75                             73B   90     100    40   100   100   100  95   50                             74B   100    100    85   95    100   100  90   80                             75B   100    100    100  70    100   100  100  95                             77B   100    100    55   40    100   100  90   70                             818   90     95     60   10    25    75   90   0                              82B   40     90     20   35    100   --   75   20                             91B   100    100    85   100   100   100  80   90                             101B  85     90     0    0     95    50   50   75                             ______________________________________                                    

                  TABLE II-C                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG   VL    MD   CD   YNS                            ______________________________________                                        1C    65     80     65   55    90    90   35   0                              ______________________________________                                    

                  TABLE II-D                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG   VL    MD   CD   YNG                            ______________________________________                                         1D   100    100    85   30    100   100  90   90                              2D   100    100    100  50    100   100  95   95                              3D   100    100    85   25    100   100  100  95                              4D   100    100    100  20    100   85   95   90                              5D   100    100    45   25    100   100  90   90                              6D   100    100    95   40    100   100  85   90                              9D   100    100    90   90    100   100  80   90                             10D   100    90     20   10    100   70   100  90                             11D   90     100    50   230   100   100  90   90                             12D   100    100    95   80    100   100  90   90                             13D   40     75     0    10    80    100  100  90                             14D   50     0      0    0     100   80   70   90                             15D   65     95     20   15    100   80   90   85                             17D   100    100    60   30    100   100  90   35                             18D   100    100    100  100   100   100  100  95                             19D   100    100    0    50    100   100  100  95                             20D   75     100    0    25    100   90   65   90                             21D   100    100    100  80    100   100  90   95                             22D   100    100    100  80    100   100  95   95                             23D   100    100    98   95    100   100  100  95                             25D   100    100    80   100   100   100  80   --                             26D   100    100    75   100   100   100  80   --                             27D   90     100    50   100   100   100  100  90                             28D   75     50     50   0     100   100  90   65                             30D   100    100    85   100   100   100  95   90                             31D   85     75     0    25    100   25   0    35                             32D   83     85     35   20    95    100  75   50                             36D   100    100    50   100   100   100  100  75                             37D   20     75     0    20    100   95   100  75                             38D   85     95     40   60    100   100  75   85                             39D   85     95     45   75    100   95   70   90                             51D   60     60     35   0     25    0    0    30                             52D   75     75     0    50    90    75   40   0                              65D   100    100    80   100   100   100  --   80                             ______________________________________                                         A blank (--) indicates that the weed was not tested.                     

                  TABLE II-E                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG   VL    MD   CD   YNG                            ______________________________________                                        1E    0      0      0    0     0     0    0    20                             2E    25     30     30   0     70    0    40   30                             3E    25     20     0    0     0     0    0    0                              4E    100    100    90   60    100   100  100  90                             5E    50     60     40   50    50    60   90   50                             6E    100    95     50   40    40    60   99   70                             16E   80     100    50   60    100   90   90   90                             20E   100    100    30   15    100   100  90   85                             21E   100    100    --   30    100   95   100  80                             ______________________________________                                         A blank (--) indicates that the weed was not tested.                     

                  TABLE II-F                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG   VL    MD   CD   YNG                            ______________________________________                                         1F   40     20     0    0     0     0    0    100                             2F   60     70     0    0     0     0    90   100                             3F   100    100    50   50    100   100  85   90                              4F   100    100    90   30    100   85   95   95                              5F   100    100    80   10    100   100  100  95                              6F   20     35     25   15    90    85   40   85                              7F   100    100    90   100   100   100  100  95                              8F   100    100    90   100   100   100  100  95                              9F   100    100    0    0     100   80   100  90                             10F   100    100    100  100   100   100  100  95                             11F   100    100    70   100   100   100  97   95                             12F   100    100    60   100   100   100  100  95                             13F   100    100    60   100   100   100  100  95                             14F   80     100    50   80    100   100  90   90                             15F   100    100    80   100   100   100  100  --                             16F   50     75     0    25    100   100  95   60                             17F   100    100    40   100   100   100  100  85                             18F   100    100    0    20    100   100  80   70                             20F   70     75     0    25    100   95   100  60                             21F   50     60     0    0     100   80   80   60                             22F   100    95     35   25    100   100  90   50                             23F   95     100    40   20    100   100  90   50                             24F   100    100    90   0     45    85   80   90                             25F   100    100    25   60    100   100  100  75                             34F   35     40     10   0     60    25   0    70                             37F   50     60     0    0     60    0    50   0                              38F   35     40     0    0     0     0    0    0                              52F   85     100    30   95    100   100  --   80                             53F   100    100    0    85    100   100  --   80                             54F   100    100    90   25    100   100  --   80                             ______________________________________                                         A blank (--) indicates that the weed was not tested.                     

                  TABLE II-G                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.    FT     WG      WO   AMG    VL   MD    YNG                              ______________________________________                                         1G    100    100     90   100    100  100   80                                2G    100    100     90   100    100  100   80                                3G    100    100     90   100    100  100   80                                4G    100    100     90   100    100  100   80                                5G    100    100     90   100    100  100   80                                6G*   100    100     100  100    100  --    20                                7G    100    100     80   100    100  100   80                                8G    85     100     80   100    100  100   80                                9G    100    100     80   100    100  100   80                               10G    100    100     80   100    100  100   80                               11G    100    100     80   100    100  100   80                               12G    100    100     80   90     100  100   0                                13G    100    100     70   100    100  100   0                                14G    100    100     75   100    100  100   90                               15G    100    100     80   100    100  100   90                               16G    100    100     90   100    100  100   80                               17G    100    100     80   100    100  100   80                               18G    100    100     90   85     100  100   80                               19G    100    100     100  100    100  100   80                               20G    70     95      10   100    100  100   0                                21G    100    100     100  100    100  100   80                               22G    100    100     90   100    100  100   80                               23G    100    100     100  100    100  100   80                               24G    0      80      0    25     80   70    0                                25G    100    100     80   100    100  100   80                               26G    100    100     100  80     100  100   80                               27G    100    100     100  100    100  100   80                               28G    100    100     90   100    100  100   80                               ______________________________________                                         A blank (--) indicates that the weed was not tested.                          *= Tested at 0.56 kg/ha.                                                 

Post-Emergence Herbicide Test

This test is conducted in an identical manner to the testing procedurefor the pre-emergence herbicide test, except the seeds of the eightdifferent weed species are planted 10-12 days before treatment. Also,watering of the treated flats is confined to the soil surface and not tothe foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in TableIII.

                                      TABLE III-A                                 __________________________________________________________________________    Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 __________________________________________________________________________    Cmpd. No.                                                                           FT WG  WO AMG  VL MD  PW CD  YNS                                        __________________________________________________________________________    1A    60 70  20 40   60 60  35     60                                         2A    30 70  0  50   90 85  30     80                                         3A    0  30  0  70   100                                                                              90  55     70                                         4A    95 98  20 98   100                                                                              100 30     95                                         5A    80 80  75 50   60 80  0      95                                         6A    40 40  10 60   100                                                                              100 75     65                                         7A    60 75  40 60   100                                                                              75  100    75                                         8A    85 80  75 70   95 80  90     90                                         9A    85 80  75 70   95 80  90     90                                         10A   95 85  90 60   95 95  80     95                                         11A   50 80  35 55   100                                                                              100 95     80                                         12A   45 75  50 55   75 60  50     80                                         13A   30 60  20 60   80 50  60     70                                         14A   20 10  20 50   45 40  40     0                                          15A   65 95  0  65   95 30  100    80                                         16A   65 80  20 85   85 30  30     80                                         17A   75 80  30 70   100                                                                              100 85     90                                         18A   100                                                                              95  10 100  100                                                                              100 100    90                                         19A   60 80  40 70   100                                                                              75  80     90                                         20A   65 80  10 85   95 95  100    70                                         21A   30 55  0  80   100                                                                              80  65     80                                         22A   0  30  0  20   45 0   30     20                                         23A   85 90  40 85   100                                                                              95  100    90                                         24A   0  80  0  70   90 74  --     100                                        25A   100                                                                              100 75 90   100                                                                              100 --     100                                        26A   45 30  0  40   70 65     0   45                                         27A   75 80  30 65   50 45     85  85                                         28A   75 60  60 75   100                                                                              70     80  25                                         29A   85 85  85 75   85 65     65  85                                         30A   75 50  20 10   0  0      20  40                                         __________________________________________________________________________    Cmpd. No.                                                                           FT WG  WO AMG  VL MD  PW CD  YNG                                        __________________________________________________________________________    31A   60 60  20 40   40 70     100 40                                         32A   60 25  20 40   90 65     20  40                                         33A   10 0   0  10   10 10     100 40                                         34A   10 10  0  5    50 30     80  0                                          35A   0  0   0  10   60 30     40  0                                          36A   0  0   0  20   20 20     0   0                                          37A   0  0   0  30   40 20     80  0                                          38A   10 10  10 20   10 20     20  10                                         39A   40 40  20 0    0  0      5   80                                         40A   90 70  40 20   60 80     20  65                                         41A   60 85  85 20   40 60     100 100                                        42A   60 50  40 70   20 40     60  60                                         43A   100                                                                              80  30 60   100                                                                              100    80  100                                        44A   80 85  0  60   90 90     100 80                                         45A   90 90  10 100  100                                                                              100    100 90                                         46A   80 100 0  60   100                                                                              100    100 100                                        47A   100                                                                              100 0  60   100                                                                              100    100 100                                        48A   40 40  20 10   10 10     90  40                                         49A   40 40  40 80   100                                                                              100    60  60                                         50A   80 60  60 50   50 60     80  70                                         51A   80 80  80 95   100                                                                              100    100 90                                         52A   60 60  20 20   40 40     90  60                                         53A   10 20  20 0    0  0      0   20                                         54A   20 40  20 5    0  0      0   40                                         55A   40 40  40 60   60 60     80  90                                         56A   100                                                                              100 75 80   100                                                                              100    100 90                                         57A   80 80  80 95   100                                                                              100    100 90                                         58A   60 70  10 70   10 10     20  80                                         59A   100                                                                              100 90 100  -- 100    100 50                                         60A   100                                                                              100 100                                                                              100  -- 100    100 70                                         61A   90 85  90 85   -- 100    100 80                                         62A   100                                                                              85  100                                                                              75   100                                                                              100    100 35                                         63A   70 80  20 100  100                                                                              100    35  40                                         64A   75 75  90 70   90 70     40  40                                         65A   100                                                                              70  100                                                                              55   90 95     100 40                                         66A   100                                                                              75  100                                                                              90   95 95     100 20                                         73A   100                                                                              100 95 100  100                                                                              100    55  30                                         74A   100                                                                              95  75 100  100                                                                              100    85  40                                         75A   100                                                                              100 30 95   80 100    80  40                                         76A   80 80  75 75   100                                                                              95     95  25                                         77A   80 80  80 90   90 80     90  80                                         78A   80 85  75 85   80 95     100 50                                         79A   50 65  35 90   100                                                                              100    90  --                                         80A   40 40  10 20   60 0      0   30                                         81A   90 70  60 40   60 60     90  70                                         84A   100                                                                              100 100                                                                              20   40 40     80  60                                         88A   100                                                                              95  90 100  85 100    100 50                                         89A   100                                                                              100 75 85   75 85     95  50                                         90A   100                                                                              85  90 90   85 90     100 55                                         91A   100                                                                              100 100                                                                              100  95 100    95  60                                         105A  35 50  -- 35   100                                                                              80     60  30                                         117A  40 60  0  25   50 50     80  --                                         118A  95 85  85 100  100                                                                              90     80  80                                         121A  65 85  40 100  100                                                                              100    60  50                                         125A  90 95  75 70   100                                                                              90     100 60                                         126A  40 50  20 40   60 50     100 80                                         127A  100                                                                              95  100                                                                              95   100                                                                              100        80                                         128A  85 95  80 60   100                                                                              95         80                                         129A  65 90  60 60   100                                                                              98         70                                         130A  100                                                                              95  95 95   100                                                                              100        70                                         131A  0  20  0  0    30 75     10  0                                          132A  95 100 100                                                                              80   95 95         50                                         133A  80 95  90 60   35 85         60                                         135A  70 100 100                                                                              75   100                                                                              95         70                                         __________________________________________________________________________

                  TABLE III-B                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                        1B    85     95      20   95    100  100   95   95                            2B    90     90      80   100   90   90    --   80                            4B    60     60      90   40    60   60    90   70                            5B    40     60      10   20    40   40    90   80                            6B    40     50      10   60    20   20    60   50                            7B    80     80      80   60    60   90    6    60                            8B    100    80      60   30    80   80    80   80                            9B    70     70      60   40    60   60    80   70                            10B   40     40      60   30    60   60    90   60                            11B   80     90      60   45    90   90    100  80                            12B   25     45      10   20    20   20    60   45                            13B   100    100     95   70    60   60    80   60                            15B   100    60      50   80    90   90    40   60                            16B   60     60      80   80    90   90    60   65                            17B   100    70      90   100   --   90    98   70                            18B   100    85      100  85    --   100   100  65                            19B   100    80      85   100   100  90    100  70                            20B   90     65      90   85    70   60    100  40                            21B   40     40      10   0     0    0     0    0                             22B   40     70      80   90    90   100   95   40                            25B   40     70      40   40    40   60    70   50                            26B   65     70      80   40    90   80    70   80                            27B   100    80      60   20    90   90    80   45                            28B   90     60      60   60    60   60    40   70                            29B   90     70      70   40    70   70    60   60                            30B   100    90      70   50    100  100   80   80                            31B   40     50      20   10    20   20    0    40                            32B   25     40      40   90    100  100   40   40                            33B   20     40      10   60    90   90    60   40                            34B   90     80      80   80    100  100   80   50                            35B   60     50      50   20    60   60    80   60                            36B   100    80      80   75    --   100   100  45                            37B   100    60      50   80    90   90    40   60                            39B   90     80      25   30    30   45    50   30                            40B   20     40      10   60    90   90    60   40                            41B   25     45      10   20    20   20    60   45                            42B   90     80      80   80    100  100   100  70                            43B   80     90      95   97    100  100   100  50                            44B   100    95      95   95    40   100   100  30                            45B   30     65      0    30    45   40    65   50                            46B   70     75      0    65    100  100   50   70                            47B   100    100     100  90    100  100   100  85                            48B   100    65      80   50    100  100   60   60                            49B   60     70      70   40    80   70    30   50                            50B   0      60      40   60    100  90    20   30                            51B   100    75      80   40    100  50    20   30                            52B   90     100     100  100   100  100   100  40                            53B   60     70      70   70    90   65    40   60                            54B   100    100     85   100   100  100   100  60                            55B   95     85      90   100   100  100   90   45                            56B   85     100     0    10    15   95    40   50                            57B   85     70      65   0     0    0     0    35                            58B   20     40      10   15    70   40    35   40                            59B   100    95      100  95    100  95    100  40                            60B   65     75      75   80    90   85    80   60                            61B   80     80      70   95    80   85    80   50                            62B   100    80      25   80    75   80    85   35                            63B   100    100     40   95    95   100   95   50                            64B   75     70      50   90    90   100   90   50                            65B   100    80      80   60    85   60    0    --                            66B   98     90      60   35    --   100   60   90                            67B   70     65      20   15    95   40    70   45                            71B   95     50      50   80    80   80    65   50                            72B   100    85      75   75    65   85    70   60                            73B   100    95      95   85    75   85    95   40                            74B   100    85      95   90    80   95    65   50                            75B   100    80      80   30    50   60    100  40                            81B   50     80      35   70    70   90    80   10                            82B   25     60      50   35    50   90    50   25                            91B   80     60      40   60    75   90    60   75                            101B  10     35      --   30    75   70    40   50                            ______________________________________                                         (--) = Specie did not germinate for some reason.                         

                  TABLE III-C                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                        1C    98     95      70   60    100  55    100  90                            ______________________________________                                    

                  TABLE III-D                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG    VL   MD   CD   YNG                            ______________________________________                                        1D    95     75     85   70     100  90   85   40                             2D    45     70     95   75     100  90   100  65                             3D    100    80     100  90     --   100  100  80                             4D    100    80     100  100    --   100  85   75                             5D    90     70     45   60     95   70   60   80                             6D    95     75     80   70     100  90   90   65                             9D    100    90     90   100    100  100  95   85                             10D   45     75     10   15     100  100  20   75                             11D   100    70     60   75     100  100  100  45                             12D   100    75     100  100    100  100  90   90                             13D   30     55     0    30     60   60   15   60                             14D   20     65     0    40     70   60   40   25                             15D   20     75     30   20     100  70   60   40                             17D   85     80     50   65     95   95   100  60                             18D   100    95     100  100    100  100  100  75                             19D   20     95     30   100    100  35   30   70                             20D   30     80     15   100    100  45   20   70                             21D   100    80     100  55     100  90   100  80                             22D   100    80     100  60     100  95   95   95                             23D   100    90     90   100    100  100  85   70                             25D   70     75     50   85     90   85   60   75                             26D   100    85     85   95     95   95   90   60                             27D   90     90     60   100    100  100  100  --                             28D   15     45     20   50     75   80   15   30                             30D   100    100    80   85     85   85   100  --                             31D   80     90     100  100    100  100  100  60                             32D   75     85     85   75     75   90   95   50                             36D   35     50     35   70     50   50   35   60                             37D   60     75     15   70     70   90   90   40                             38D   95     90     65   70     90   90   100  50                             39D   95     85     30   50     70   80   100  50                             51D   60     75     60   35     30   60   40   60                             52D   60     75     25   100    100  100  100  75                             65D   70     50     70   90     80   85   --   80                             ______________________________________                                         A blank (--) indicates the weed was not tested.                          

                  TABLE III-E                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG    VL   MD   CD   YNG                            ______________________________________                                        1E    20     20     10   20     40   40   20   40                             2E    0      60     60   50     70   30   0    15                             3E    20     20     0    10     0    20   0    20                             4E    85     90     100  45     75   30   80   65                             5E    55     50     60   50     75   85   65   --                             6E    70     70     50   60     80   70   90   --                             16E   95     95     40   100    100  100  100  90                             20E   95     75     35   40     95   75   35   80                             21E   80     70     30   45     80   90   50   70                             ______________________________________                                         A blank (--) indicates the weed was not tested.                          

                  TABLE III-F                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG    VL   MD   CD   YNG                            ______________________________________                                        1F    60     40     20   30     40   40   50   60                             2F    50     40     10   20     20   20   40   60                             3F    100    100    85   100    100  100  100  75                             4F    100    100    95   85     100  95   100  60                             5F    95     95     100  65     90   25   70   45                             6F    40     30     0    20     90   25   20   70                             7F    100    100    100  100    100  100  100  90                             8F    100    95     100  100    100  100  100  70                             9F    65     65     0    20     80   65   90   80                             10F   100    100    100  100    100  100  100  70                             11F   85     90     90   85     90   80   30   60                             12F   100    90     65   80     100  100  100  50                             13F   100    95     100  100    100  100  90   --                             14F   100    100    100  100    100  100  100  50                             15F   25     35     15   30     80   25   20   0                              16F   100    85     70   75     90   90   50   --                             17F   100    100    100  100    100  100  100  --                             18F   90     85     85   85     90   95   70   40                             20F   40     60     10   60     100  100  100  50                             21F   35     60     10   60     100  100  80   60                             22F   95     95     35   100    100  100  90   50                             23F   100    100    40   100    100  100  90   50                             24F   100    75     100  60     --   100  100  60                             25F   95     95     90   95     100  100  95   35                             34F   50     40     0    35     50   70   30   50                             37F   20     60     0    30     30   50   50   50                             38F   25     50     0    25     25   50   20   20                             52F   0      60     50   50     10   50   --   20                             53F   0      50     0    50     50   50   --   30                             54F   90     75     60   50     50   80   --   80                             ______________________________________                                         A blank (--) indicates the weed was not tested.                          

                  TABLE III-G                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.     FT      WG     WO   AMG   VL    MD   YNG                              ______________________________________                                         1G     100     95     90   90    100   100  80                                2G     100     100    100  100   100   100  80                                3G     100     100    95   100   100   100  90                                4G     100     100    100  100   100   100  90                                5G     100     100    100  100   100   100  100                               6G*    10      80     50   75    40    --   0                                 7G     70      75     70   90    90    80   80                                8G     50      80     70   90    90    80   30                                9G     70      80     70   90    90    80   30                               10G     75      80     70   80    60    50   70                               11G     70      80     70   80    80    80   80                               12G     100     75     90   75    80    80   80                               13G     60      70     70   100   100   100  80                               14G     20      70     40   60    80    80   70                               15G     90      70     70   75    80    90   70                               16G     50      70     80   60    80    90   70                               17G     90      60     70   65    80    80   80                               18G     30      50     80   95    95    80   70                               19G     100     100    95   90    100   100  80                               20G     10      40     5    70    80    90   70                               21G     95      90     95   95    100   100  70                               22G     80      90     90   80    100   100  70                               23G     90      80     80   80    90    80   30                               24G     0       30     0    40    80    20   0                                25G     0       20     0    10    10    20   0                                26G     80      70     70   80    80    80   70                               27G     90      90     90   80    80    90   60                               28G     70      65     50   80    80    80   70                               ______________________________________                                         A blank (--) indicates the weed was not tested.                               * = Tested at 0.56 kg/ha.                                                

Pre-Emergence Multi-Weed Herbicide Test

Several compounds were evaluated at an application rate of 2 lb/acre(2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for pre-emergence activityagainst a larger number of weed species.

The process was generally similar to the pre-emergence herbicide testdescribed above except that only 300 or 150 milligrams of test compoundwere weighed out and the application rate was 40 gallons per acre.

Redroot pigweed (PW) and curly dock (CD) were eliminated in this testand the following weed species were added:

    ______________________________________                                        Grasses:                                                                             downy brome    Bromus tectorum                                                                             (DB)                                             annual ryegrass                                                                              Lolium multiflorum                                                                          (ARG)                                            rox-orange sorghum                                                                           Sorghum bicolor                                                                             (SHC)                                            hemp sesbania  Sesbania exaltata                                                                           (SESB)                                           nightshade     Solanum sp.   (SP)                                             cocklebur      Xattiium sp.  (CB)                                      ______________________________________                                    

The results of the 2.24 kg/ha test are shown in Table IV and the resultsof the 1.12 kg/ha test are shown in Table VI.

Post-Emergence Multi-Weed Herbicide Test

Several compounds were evaluated at an application rate of 2 lb/acre(2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for post-emergence activityagainst the larger number of weed species that are used in thepre-emergent multi-herbicide test.

The process was generally similar to the post-emergence herbicide testdescribed above except that only 300 or 150 milligrams of test compoundwere weighed out and the application rate was 40 gallons per acre.

The results of the 2.24 kg/ha test are shown in Table V and the resultsfor the 1.12 kg/ha test are shown in Table VII.

                                      TABLE IV-A                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    67A 20 90 25  98 80 60 90 45  90  45 20 85 85 15                              68A 65 98 98  100                                                                              100                                                                              60 95 100 100 100                                                                              80 100                                                                              95 100                             69A 65 100                                                                              70  100                                                                              100                                                                              65 95 100 95  70 65 100                                                                              90 --                              70A 98 100                                                                              100 100                                                                              100                                                                              90 98 90  100 90 60 100                                                                              95 80                              71A 60 20 100 100                                                                              100                                                                              80 95 35  40  100                                                                              20 90 100                                                                              40                              72A 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 90  100                                                                              60 100                                                                              100                                                                              20                              83A 15 45 25  90 15 5  90 45  35  20 0  20 75 --                              86A 20 0  15  60 60 20 70 25  45  100                                                                              20 100                                                                              15 35                              87A 100                                                                              90 85  100                                                                              85 25 30 35  85  100                                                                              85 100                                                                              95 40                              __________________________________________________________________________

                                      TABLE VI-A                                  __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    86A 60 100                                                                              50  90 50 60 90 70  100 100                                                                              20 100                                                                              20 --                              87A 95 100                                                                              30  100                                                                              80 70 80 95  100 100                                                                              100                                                                              100                                                                              70 --                              __________________________________________________________________________

                                      TABLE V-A                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________     82A                                                                              35 100                                                                              85  100                                                                              65 60 90 50  90  60 30 97 90 40                               85A                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              85 100                                                                              20  10  100                                                                              65 100                                                                              100                                                                              30                               92A                                                                              15 20 45  100                                                                              90 40 80 95  95  100                                                                              25 100                                                                              90 40                               93A                                                                              30 75 40  100                                                                              100                                                                              60 90 100 100 100                                                                              35 100                                                                              90 40                               94A                                                                              30 70 40  100                                                                              100                                                                              30 65 95  85  100                                                                              0  100                                                                              90 30                               95A                                                                              0  0  0   85 60 15 70 65  60  100                                                                              80 90 10 20                               96A                                                                              95 100                                                                              98  100                                                                              100                                                                              70 100                                                                              100 95  90 80 100                                                                              95 --                               97A                                                                              100                                                                              100                                                                              98  100                                                                              100                                                                              100                                                                              100                                                                              100 95  100                                                                              70 100                                                                              95 100                              98A                                                                              10 0  0   0  20 25 70 0   20  0  0  80 30 --                               99A                                                                              15 0  0   75 25 0  20 30  60  15 20 30 25 0                               100A                                                                              0  0  0   0  0  0  20 10  0   0  0  15 0  --                              101A                                                                              100                                                                              98 95  100                                                                              100                                                                              70 98 100 100 100                                                                              20 100                                                                              95 --                              102A                                                                              25 20 35  100                                                                              100                                                                              45 95 70  100 100                                                                              60 100                                                                              90 --                              103A                                                                              80 60 45  100                                                                              100                                                                              40 90 65  90  100                                                                              0  100                                                                              95 0                               106A                                                                              100                                                                              100                                                                              60  40 95 35 100                                                                              35  90  100                                                                              70 100                                                                              90 --                              107A                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              90 100                                                                              100 100 100                                                                              80 100                                                                              95 30                              108A                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              85 100                                                                              100 100 100                                                                              30 100                                                                              95 100                             109A.sup.a                                                                        65 20 85  100                                                                              98 60 90 30  50  100                                                                              50 100                                                                              90 100                             110A                                                                              0  60 30  100                                                                              65 25 65 25  30  100                                                                              0  100                                                                              60 0                               111A                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              75 98 100 100 100                                                                              90 100                                                                              -- 70                              112A                                                                              100                                                                              100                                                                              90  100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              100                                                                              100                                                                              -- --                              113A                                                                              65 95 40  100                                                                              100                                                                              30 90 70  100 100                                                                              0  100                                                                              -- 30                              114A                                                                              70 100                                                                              25  100                                                                              100                                                                              40 100                                                                              100 100 100                                                                              30 100                                                                              95 80                              115A                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              45 100                                                                              85 100                             116A                                                                              25 15 20  100                                                                              65 35 65 45  50  100                                                                              0  100                                                                              95 10                              119A                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              95 100                                                                              95 90                              120A                                                                              100                                                                              100                                                                              100 100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              100                                                                              100                                                                              90 100                             122A                                                                              80 80 45  100                                                                              60 65 70 100 100 100                                                                              100                                                                              100                                                                              90 100                             123A                                                                              0  100                                                                              50  100                                                                              85 0  60 100 90  100                                                                              80 100                                                                              100                                                                              20                              124A                                                                              25 50 65  90 65 0  40 75  80  100                                                                              40 90 80 60                              __________________________________________________________________________     .sup.a application rate was 0.56 kg/ha.                                  

                                      TABLE VII-A                                 __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________     82A                                                                              60 40 10  98 35 10 30 70  100 100                                                                              100                                                                              90 45 --                               85A                                                                              60 60 35  100                                                                              45 60 85 50  100 100                                                                              100                                                                              100                                                                              60 --                               92A                                                                              70 55 20  80 80 45 100                                                                              95  90  80 20 95 70 90                               93A                                                                              90 90 70  95 95 75 90 98  95  85 35 100                                                                              60 90                               94A                                                                              100                                                                              85 45  90 100                                                                              90 100                                                                              100 90  90 30 100                                                                              60 85                               95A                                                                              20 60 0   80 70 0  45 60  75  90 0  65 20 --                               96A                                                                              95 100                                                                              90  95 100                                                                              80 95 100 100 100                                                                              70 100                                                                              70 90                               97A                                                                              100                                                                              100                                                                              95  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              90 100                                                                              70 100                              98A                                                                              20 0  0   45 10 50 30 20  65  100                                                                              0  75 35 80                               99A                                                                              25 75 15  80 65 10 25 85  100 100                                                                              80 100                                                                              10 --                              100A                                                                              10 35 0   70 50 5  20 30  70  40 0  100                                                                              10 100                             101A                                                                              30 60 25  100                                                                              60 60 80 100 100 100                                                                              30 100                                                                              70 --                              103A                                                                              90 100                                                                              25  100                                                                              100                                                                              80 100                                                                              100 100 100                                                                              15 100                                                                              40 --                              104A                                                                              98 98 25  98 100                                                                              15 100                                                                              100 100 100                                                                              60 100                                                                              95 --                              106A                                                                              75 90 30  90 70 25 100                                                                              100 100 100                                                                              80 100                                                                              75 --                              107A                                                                              100                                                                              100                                                                              80  90 85 100                                                                              100                                                                              100 100 100                                                                              60 100                                                                              40 --                              108A                                                                              100                                                                              100                                                                              65  90 60 95 100                                                                              100 100 100                                                                              90 100                                                                              90 --                              109A.sup.a                                                                        90 60 45  90 70 60 98 95  95  100                                                                              98 80 55 --                              110A                                                                              50 50 20  100                                                                              50 10 40 100 98  98 20 100                                                                              35 45                              111A                                                                              85 90 80  90 70 60 95 100 90  100                                                                              65 100                                                                              80 60                              112A                                                                              100                                                                              100                                                                              90  100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              45 100                                                                              95 70                              113A                                                                              70 50 20  90 60 50 80 95  95  100                                                                              60 100                                                                              -- 60                              114A                                                                              85 100                                                                              15  100                                                                              100                                                                              60 00 100 100 100                                                                              100                                                                              100                                                                              60 --                              115A                                                                              100                                                                              100                                                                              45  100                                                                              100                                                                              80 100                                                                              100 100 100                                                                              100                                                                              100                                                                              90 --                              116A                                                                              80 60 25  90 35 40 45 75  90  100                                                                              40 90 75 60                              119A                                                                              60 70 30  95 70 20 90 100 100 100                                                                              90 100                                                                              30 85                              120A                                                                              75 90 60  95 80 45 100                                                                              100 90  100                                                                              65 100                                                                              35 100                             122A                                                                              60 90 15  100                                                                              30 15 15 100 100 100                                                                              75 100                                                                              45 95                              123A                                                                              0  100                                                                              35  100                                                                              50 15 85 100 100 100                                                                              100                                                                              100                                                                              70 85                              124A                                                                              25 100                                                                              35  40 35 0  40 95  100 100                                                                              100                                                                              100                                                                              85 75                              __________________________________________________________________________     .sup.a Application rate was 0.56 kg/ha.                                  

A dash mark (--) is used in Tables II-VII to indicate that no percentcontrol number was available.

                                      TABLE IV-B                                  __________________________________________________________________________    Pre-Emergence Multi-Weed Herbicide Test                                       Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS CB                             __________________________________________________________________________    14B 80 100                                                                              100 100                                                                              100                                                                              80 95 70  60  100                                                                              40 85 100 10                             21B 85 100                                                                              90  100                                                                              100                                                                              85 100                                                                              100 100 100                                                                              70 100                                                                              95  100                            24B 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              75 100                                                                              95  --                             38B 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              20  10  100                                                                              20 95 100 20                             88B 75 100                                                                              60  100                                                                              100                                                                              70 60 20  40  100                                                                              0  100                                                                              60  20                             89B 20 60 30  85 95 55 40 15  20  65 0  100                                                                              35  50                             90B 60 100                                                                              60  100                                                                              100                                                                              45 30 100 100 100                                                                              15 100                                                                              50  85                             103B                                                                              95 100                                                                              75  100                                                                              100                                                                              50 85 100 100 100                                                                              80 100                                                                              80  40                             104B                                                                              60 100                                                                              60  100                                                                              100                                                                              45 30 100 100 100                                                                              15 100                                                                              50  85                             __________________________________________________________________________     -- = Specie did not germinate for some reason.                           

                                      TABLE V-B                                   __________________________________________________________________________    Post-Emergence Multi-Weed Herbicide Test                                      Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS CB                             __________________________________________________________________________    24B 35 25 45  60 65 85 90 100 100 -- 90 100                                                                              65  --                             88B 60 30 30  90 100                                                                              80 100                                                                              100 100 100                                                                              30 100                                                                              20  100                            89B 50 70 35  90 60 35 20 100 90  100                                                                              35 100                                                                              15  100                            90B 30 100                                                                              40  100                                                                              70 10 25 100 100 100                                                                              30 90 50  95                             103B                                                                              95 100                                                                              70  100                                                                              65 75 65 100 100 100                                                                              65 100                                                                              50  100                            104B                                                                              30 100                                                                              40  100                                                                              70 10 25 100 100 100                                                                              30 90 50  95                             __________________________________________________________________________     -- = Specie did not germinate for some reason.                           

                                      TABLE VI-B                                  __________________________________________________________________________    Pre-Emergence Multi-Weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No.  DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS CB                            __________________________________________________________________________     1B  25 10 30  85 55 0  -- 55  --  100                                                                              -- 75 75  35                            23B  55 95 90  100                                                                              95*                                                                              95 95 98  80  -- 10 100                                                                              95  --                            68B  65 100                                                                              60  100                                                                              100*                                                                             6  90 100 90  100                                                                              20 100                                                                              30  40                            69B  70 100                                                                              60  100                                                                              100*                                                                             95 95 100 95  100                                                                              0  100                                                                              85  25                            70B  60 100                                                                              75  100                                                                              100*                                                                             85 100                                                                              100 90  100                                                                              25 100                                                                              90  25                            76B  100                                                                              100                                                                              85  100                                                                              100*                                                                             85 98 100 95  -- 35 100                                                                              95  --                            78B  40 70 15  95 75*                                                                              25 80 65  75  -- 0  100                                                                              80  --                            79B  100                                                                              100                                                                              100 100                                                                              100                                                                              98 100                                                                              100 85  100                                                                              85 100                                                                              95  --                            80B  98 100                                                                              95  100                                                                              100                                                                              60 98 99  90  100                                                                              35 100                                                                              85  --                            83B  20 100                                                                              60  100                                                                              100*                                                                             40 90 85  65  100                                                                              0  100                                                                              85  --                            84B  0  90 25  98 100*                                                                             30 90 20  35  100                                                                              5  100                                                                              50  --                            85B  80 100                                                                              50  100                                                                              100                                                                              60 90 100 90  100                                                                              0  100                                                                              95  --                            86B  60 90 40  100                                                                              100                                                                              60 70 35  60  100                                                                              100                                                                              100                                                                              --  --                            87B  0  90 15  100                                                                              85 15 70 40  60  100                                                                              40 90 20  --                            92B  20 40 10  95 40 10 60 65  30  100                                                                              0  55 60  0                             93B  60 95 20  100                                                                              100                                                                              75 100                                                                              100 100 100                                                                              0  100                                                                              40  35                            94B  0  80 40  100                                                                              95 25 85 80  40  100                                                                              10 85 55  10                            95B  98 100                                                                              30  100                                                                              100                                                                              40 90 100 100 100                                                                              40 100                                                                              90  30                            96B  100                                                                              100                                                                              75  100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              60 100                                                                              85  100                           97B  100                                                                              100                                                                              90  100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              60 100                                                                              95  100                           98B  95 100                                                                              100 100                                                                              100                                                                              80 100                                                                              100 100 100                                                                              50 100                                                                              100 60                             99B**                                                                             -- 100                                                                              75  100                                                                              100*                                                                             20 75 50  75  95 0  -- 85  30                            100B 100                                                                              98 98  100                                                                              100                                                                              90 95 100 75  100                                                                              70 100                                                                              95  40                            102B 0  100                                                                              25  100                                                                              90 75 95 60  60  100                                                                              30 100                                                                              90  --                            __________________________________________________________________________     * = seedling johnsongrass (Sorghum halepense) was substituted for             roxorange sorghum.                                                            ** = Application rate was 0.56 kg/ha                                          -- = Specie did not germinate for some reason.                           

                                      TABLE VII-B                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicide Test                                      Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No.  DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS CB                            __________________________________________________________________________     1B  45 35 40  90 35 10 -- 60  --  75 -- 60 50  55                            23B  90 100                                                                              80  90 90*                                                                              90 90 80  90  90 40 70 25  --                            68B  50 60 40  85 80*                                                                              75 100                                                                              95  90  85 55 100                                                                              40  --                            69B  70 80 35  90 90*                                                                              80 90 80  85  90 20 90 25  --                            70B  100                                                                              90 80  100                                                                              100*                                                                             95 100                                                                              100 95  80 30 75 45  90                            76B  100                                                                              100                                                                              98  100                                                                              100*                                                                             100                                                                              100                                                                              100 100 100                                                                              60 100                                                                              40  --                            78B  100                                                                              90 80  85 100*                                                                             70 90 100 100 100                                                                              0  90 45  --                            79B  80 35 45  70 60*                                                                              70 70 45  98  100                                                                              35 90 20  --                            80B  60 70 25  90 60*                                                                              60 85 70  90  100                                                                              15 100                                                                              25  100                           85B  95 100                                                                              65  100                                                                              80 90 100                                                                              100 100 100                                                                              25 100                                                                              85  --                            86B  30 60 20  75 50 50 60 50  65  100                                                                              10 100                                                                              20  80                            87B  0  0  0   100                                                                              45 20 30 60  90  80 0  100                                                                              30  45                            92B  20 80 10  85 15 0  30 100 40  100                                                                              0  60 60  30                            93B  70 100                                                                              25  100                                                                              100                                                                              85 100                                                                              100 100 100                                                                              100                                                                              100                                                                              80  --                            94B  20 70 30  90 80 30 20 100 100 100                                                                              60 30 30  100                           95B  60 90 15  95 95 25 90 100 100 100                                                                              75 100                                                                              70  100                           96B  50 80 0   90 70 30 100                                                                              100 100 100                                                                              40 100                                                                              20  100                           97B  65 100                                                                              35  100                                                                              75 70 80 100 100 100                                                                              50 100                                                                              50  100                           98B  95 100                                                                              65  95 90 100                                                                              95 100 100 90 40 80 60  95                             99B**                                                                             -- 100                                                                              95  90 90*                                                                              90 100                                                                              25  80  40 100                                                                              -- 35  75                            100B 65 75 60  80 75 60 85 100 100 100                                                                              45 100                                                                              65  60                            102B 30 75 20  80 60 0  40 70  100 100                                                                              30 100                                                                              75  --                            __________________________________________________________________________     * = Seedling johnsongrass (Sorghum halepense) was substituted for             roxorange sorghum.                                                            ** = Application rate was 0.56 kg/ha.                                         -- = Specie did not germinate for some reason.                           

                                      TABLE IV-C                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS CB                             __________________________________________________________________________    2C  0  100                                                                              0   100                                                                              -- 45 70 65  50  100                                                                              15 100                                                                              90  --                             __________________________________________________________________________     -- = Not tested.                                                         

                                      TABLE V-C                                   __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS CB                             __________________________________________________________________________    2D  0  30 0   100                                                                              -- 0  60 85  95  100                                                                              100                                                                              90 40  --                             __________________________________________________________________________     -- = Not tested.                                                         

                                      TABLE IV-D                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________     7D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              95  100                             8D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              95  --                             .sup. 16D.sup.a                                                                   70 100                                                                              65  100                                                                              100                                                                              60 98 55  100 100                                                                              90 100                                                                              90  --                             24D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100 --                             29D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              30 100                                                                              95  80                             33D 75 15 60  90 90 20 95 100 100 100                                                                              60 100                                                                              95  100                            53D 100                                                                              100                                                                              100 100                                                                              100                                                                              90 100                                                                              100 100 100                                                                              100                                                                              100                                                                              95  100                            57D 100                                                                              100                                                                              25  100                                                                              100                                                                              30 25 100 100 100                                                                              100                                                                              100                                                                              95  100                            .sup. 64D.sup.a                                                                   -- 0  0   95 35 0  15 50  75  75 25 -- 75  40                             .sup. 66D.sup.a                                                                   -- 0  15  15 50 20 50 100 100 75 0  -- 90  100                            .sup. 67D.sup.a                                                                   -- 0  0   100                                                                              100                                                                              0  25 95  75  50 25 -- 30  75                             .sup. 69D.sup.a                                                                   -- 30 0   100                                                                              100                                                                              0  70 100 100 100                                                                              35 -- 95  100                            .sup. 70D.sup.a                                                                   -- 100                                                                              10  100                                                                              100                                                                              25 65 100 100 100                                                                              0  -- 95  100                            __________________________________________________________________________     -- = Not tested.                                                              .sup.a = Tested at 0.28 kg/ha.                                           

                                      TABLE V-D                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________    34D 90 85 30  95 -- 45 98 75  100 100                                                                              40 100                                                                              50  --                             35D 100                                                                              85 70  100                                                                              -- 90 100                                                                              100 100 100                                                                              40 100                                                                              75  --                             40D 100                                                                              100                                                                              20  100                                                                              -- 70 100                                                                              98  98  100                                                                              20 100                                                                              50  --                             41D 100                                                                              100                                                                              80  100                                                                              -- 60 100                                                                              100 100 100                                                                              25 100                                                                              95  --                             42D 50 60 40  85 -- 30 100                                                                              100 100 100                                                                              100                                                                              100                                                                              90  --                             43D 90 95 60  100                                                                              -- 30 98 100 98  100                                                                              45 100                                                                              95  --                             44D 60 100                                                                              20  100                                                                              -- 60 100                                                                              100 90  100                                                                              20 100                                                                              80  --                             45D 95 100                                                                              35  100                                                                              -- 60 90 100 100 100                                                                              0  100                                                                              90  --                             46D 100                                                                              100                                                                              90  100                                                                              -- 95 100                                                                              100 100 100                                                                              40 100                                                                              95  --                             47D 100                                                                              100                                                                              100 100                                                                              -- 98 100                                                                              100 98  100                                                                              30 100                                                                              95  --                             48D 100                                                                              100                                                                              100 100                                                                              -- 100                                                                              100                                                                              100 100 100                                                                              90 100                                                                              100 --                             49D 100                                                                              100                                                                              100 100                                                                              -- 100                                                                              100                                                                              100 100 100                                                                              90 100                                                                              --  --                             50D 100                                                                              100                                                                              100 100                                                                              100                                                                              85 100                                                                              100 100 100                                                                              90 100                                                                              98  --                             54D 100                                                                              100                                                                              85  100                                                                              100                                                                              15 100                                                                              25  100 100                                                                              65 100                                                                              95  100                            55D 85 100                                                                              35  100                                                                              98 15 100                                                                              15  100 100                                                                              65 100                                                                              95  --                             56D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100 100                            58D 98 100                                                                              40  95 40 20 95 100 100 100                                                                              85 100                                                                              100 95                             59D 100                                                                              100                                                                              100 100                                                                              100                                                                              90 100                                                                              100 100 100                                                                              100                                                                              100                                                                              85  80                             60D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              75 100                                                                              85  80                             __________________________________________________________________________     -- = Not tested.                                                         

                                      TABLE VI-D                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 0.56 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________    61D -- 100                                                                              65  100                                                                              65 20 80 20  40  80 10 -- 20  0                              62D -- 50 35  70 50 0  0  0   25  50 0  -- 0   0                              63D 100                                                                              100                                                                              100 100                                                                              100                                                                              95 100                                                                              90  95  100                                                                              75 100                                                                              100 85                             68D -- 0  20  0  0  0  0  60  100 100                                                                              90 -- 75  75                             71D -- 50 40  50 75 40 35 75  50  70 0  -- 75  75                             72D -- 35 60  100                                                                              85 50 100                                                                              25  65  100                                                                              35 -- 100 35                             73D -- 90 70  100                                                                              95 25 0  70  100 100                                                                              0  -- 50  25                             __________________________________________________________________________     -- = Not tested.                                                         

                                      TABLE VII-D                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________     7D 100                                                                              100                                                                              100 100                                                                              80 90 10 95  100 100                                                                              55 100                                                                              45  100                            .sup. 16D.sup.a                                                                   100                                                                              85 35  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              85  70                             24D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100 --                             29D 100                                                                              100                                                                              60  100                                                                              90 100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100 --                             33D 90 98 85  100                                                                              100                                                                              80 100                                                                              100 100 100                                                                              90 100                                                                              90  100                            53D 100                                                                              100                                                                              60  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100 --                             57D 25 40 10  100                                                                              10 0  10 100 95  100                                                                              35 100                                                                              --  100                            .sup.  64D.sup.a                                                                  -- 0  0   90 0  0  85 40  100 80 50 -- 35  100                            .sup. 66D.sup.a                                                                   -- 0  0   65 0  0  70 75  80  75 0  -- 25  75                             .sup. 67D.sup.a                                                                   -- 0  0   75 35 0  40 70  80  60 0  -- 0   100                            .sup. 69D.sup.a                                                                   -- 0  0   80 35 0  100                                                                              90  100 100                                                                              40 -- 35  100                            .sup. 70D.sup.a                                                                   -- 100                                                                              0   100                                                                              70 90 90 100 100 100                                                                              30 -- 25  100                            __________________________________________________________________________     -- = Not tested.                                                              .sup.a = Tested at 0.28 kg/ha.                                           

                                      TABLE VIII-D                                __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________    34D 90 85 30  95 -- 45 98 75  100 100                                                                              40 100                                                                              50  --                             35D 100                                                                              85 70  100                                                                              -- 90 100                                                                              100 100 100                                                                              40 100                                                                              75  --                             40D 75 100                                                                              5   100                                                                              -- 50 75 100 100 100                                                                              40 100                                                                              30  --                             41D -- -- --  -- -- -- -- --  --  -- -- -- --  --                             42D 40 100                                                                              35  100                                                                              -- 50 80 100 100 100                                                                              80 100                                                                              70  --                             43D 60 70 20  100                                                                              -- 55 60 100 100 100                                                                              95 100                                                                              70  --                             44D -- -- --  -- -- -- -- --  --  -- -- -- --  --                             45D -- -- --  -- -- -- -- --  --  -- -- -- --  --                             46D -- -- --  -- -- -- -- --  --  -- -- -- --  --                             47D 90 100                                                                              35  100                                                                              -- 75 90 100 100 100                                                                              25 100                                                                              45  --                             48D 80 100                                                                              60  100                                                                              -- 60 80 100 100 100                                                                              85 100                                                                              60  --                             49D -- -- --  -- -- -- -- --  --  -- -- -- --  --                             50D 90 80 60  95 80 90 100                                                                              100 100 100                                                                              65 100                                                                              80  --                             54D 35 50 30  100                                                                              30 15 90 100 100 100                                                                              100                                                                              100                                                                              95  --                             55D 100                                                                              100                                                                              20  100                                                                              90 20 100                                                                              90  100 100                                                                              100                                                                              100                                                                              --  --                             56D 75 90 75  95 90 25 100                                                                              100 100 100                                                                              90 100                                                                              90  100                            58D 70 100                                                                              40  100                                                                              95 30 95 100 95  100                                                                              95 100                                                                              95  85                             59D 90 100                                                                              95  100                                                                              100                                                                              50 100                                                                              100 100 100                                                                              95 100                                                                              100 95                             60D 95 100                                                                              100 100                                                                              100                                                                              75 95 100 100 100                                                                              95 100                                                                              100 100                            __________________________________________________________________________     -- = Not tested.                                                         

                                      TABLE IX-D                                  __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate - 0.56 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________    61D -- 40 0   50 35 0  40 75  95  100                                                                              0  -- 25  50                             62D -- 35 0   20 0  0  20 35  60  100                                                                              0  -- 0   100                            63D 100                                                                              100                                                                              85  98 85 100                                                                              100                                                                              100 100 100                                                                              100                                                                              85 85  95                             68D -- 30 40  85 0  25 60 80  95  100                                                                              95 -- 0   80                             71D -- 50 0   80 65 0  75 100 80  100                                                                              50 -- 25  100                            72D -- 90 70  80 50 50 75 85  100 100                                                                              90 -- 100 100                            73D -- 100                                                                              15  100                                                                              75 75 85 100 100 90 60 -- 80  100                            __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE IV-E                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG JG                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG                                 __________________________________________________________________________    17E 95 85 35  100                                                                              85                                                                              25 90 100 100 100                                                                              40 100                                                                              95                                  18E 0  0  0   50 20                                                                              0  15 60  45  100                                                                              0  100                                                                              --                                  __________________________________________________________________________

                                      TABLE V-E                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG                                __________________________________________________________________________     7E 30 70 20  100                                                                              75 0  90 100 95  100                                                                              100                                                                              100                                                                              90                                  8E 95 95 45  100                                                                              98 25 90 100 95  100                                                                              90 100                                                                              90                                  9E 10 70 40  100                                                                              20 0  80 100 85  100                                                                              40 100                                                                              95                                 10E 100                                                                              100                                                                              10  100                                                                              40 0  90 100 100 100                                                                              80 100                                                                              100                                11E 90 100                                                                              90  100                                                                              100                                                                              65 100                                                                              100 90  100                                                                              30 100                                                                              65                                 12E 100                                                                              100                                                                              80  100                                                                              100                                                                              85 90 100 100 100                                                                              85 100                                                                              90                                 13E 0  100                                                                              10  100                                                                              100                                                                              80 70 80  90  100                                                                              70 100                                                                              80                                 15E 0  10 0   90 0  0  15 35  30  100                                                                              10 85 75                                 19E 100                                                                              90 0   100                                                                              20 10 40 95  100 100                                                                              100                                                                              100                                                                              65                                 __________________________________________________________________________

                                      TABLE VI-E                                  __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG JG                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG                                 __________________________________________________________________________    17E 80 100                                                                              55  95 90                                                                              20 60 100 100 100                                                                              75 100                                                                              70                                  18E 0  100                                                                              0   98 20                                                                              0  10 70  60  100                                                                              10 100                                                                              45                                  __________________________________________________________________________

                                      TABLE VII-E                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG                                __________________________________________________________________________     7E 25 30 0   70 60 20 90 75  95  85 50 100                                                                              35                                  8E 80 80 20  70 70 40 80 50  80  80 60 60 35                                  9E 0  30 0   75 15 25 100                                                                              95  100 100                                                                              60 100                                                                              25                                 10E 60 80 20  70 35 25 80 75  90  90 70 100                                                                              45                                 11E 45 100                                                                              20  100                                                                              100                                                                              40 50 100 100 100                                                                              20 100                                                                              35                                 12E 70 60 30  100                                                                              100                                                                              80 98 90  100 100                                                                              70 98 40                                 13E 25 100                                                                              10  100                                                                              100                                                                              85 100                                                                              80  100 100                                                                              10 90 25                                 15E 30 65 10  90 50 30 20 85  80  98 30 65 15                                 19E 20 60 10  90 10 15 90 100 100 70 100                                                                              40 85                                 __________________________________________________________________________

                                      TABLE IV-F                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________    19F 40 35 60  100                                                                              90 30 90 100 100 -- 20 100                                                                              90  --                             26F 25 70 45  95 60 25 85 35  75  -- 20 100                                                                              95  90                             27F 45 65 40  100                                                                              60 25 80 100 85  100                                                                              40 100                                                                              95  35                             28F 80 100                                                                              90  100                                                                              100                                                                              90 100                                                                              70  90  100                                                                              30 100                                                                              95  35                             29F 90 45 75  100                                                                              85 40 90 95  90  100                                                                              40 100                                                                              95  --                             30F 90 45 75  100                                                                              90 75 100                                                                              100 80  100                                                                              60 100                                                                              95  --                             31F 60 65 75  100                                                                              100                                                                              55 95 100 100 100                                                                              100                                                                              100                                                                              95  --                             32F 90 100                                                                              90  100                                                                              100                                                                              65 85 100 90  100                                                                              95 100                                                                              85  --                             33F 100                                                                              100                                                                              95  100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              25 100                                                                              90  --                             35F 90 100                                                                              100 100                                                                              -- 90 90 100 90  100                                                                              10 100                                                                              75  --                             36F 90 35 85  100                                                                              -- 15 80 95  90  100                                                                              50 100                                                                              95  --                             39F 100                                                                              100                                                                              100 100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              100                                                                              100                                                                              98  --                             40F 100                                                                              100                                                                              80  100                                                                              100                                                                              70 100                                                                              100 100 100                                                                              90 100                                                                              95  --                             41F 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              60 100                                                                              98  --                             42F 60 100                                                                              85  100                                                                              100                                                                              70 95 100 95  100                                                                              10 100                                                                              95  50                             43F 85 100                                                                              25  100                                                                              60 25 98 100 100 100                                                                              100                                                                              100                                                                              90  100                            44F 0  80 10  85 0  0  75 0   30  100                                                                              0  100                                                                              0   10                             45F 25 100                                                                              40  100                                                                              60 0  65 60  60  100                                                                              50 100                                                                              70  0                              50F -- 100                                                                              50  100                                                                              35 35 75     100 100                                                                              --                                       __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE V-F                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Appication Rate - 0.56 kg/ha                                                  Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________    46F 0  65 35  75 65 0  0  0   35  100                                                                              25 90 80  0                              47F -- 60 35  100                                                                              100                                                                              0  90 100 100 100                                                                              70 -- 100 75                             48F -- 75 20  90 60 0  15 70  35  90 0  -- 20  40                             49F -- 60 10  100                                                                              60 0  50 100 95  100                                                                              40 -- 90  100                            51F -- 40 10  95 40 10 50 65  100 100                                                                              0  -- 95  65                             __________________________________________________________________________     (--)  Not tested.                                                        

                                      TABLE VI-F                                  __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                Application Rate -- 2.24 kg/ha                                                Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                             __________________________________________________________________________    19F 100                                                                              90 65  100                                                                              100                                                                              98 100                                                                              100 100 100                                                                              60 100                                                                              70  100                            26F 60 75 60  95 45 50 90 50  90  100                                                                              40 90 60  --                             27F 80 70 65  95 100                                                                              90 100                                                                              100 100 100                                                                              85 100                                                                              75  --                             28F 80 100                                                                              75  90 85 80 100                                                                              80  80  100                                                                              30 100                                                                              85  85                             29F 85 70 55  90 98 90 100                                                                              100 100 100                                                                              35 100                                                                              60  100                            30F 90 80 40  90 85 80 80 70  100 100                                                                              20 100                                                                              40  --                             31F 100                                                                              80 20  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              85  --                             32F 70 90 60  100                                                                              100                                                                              98 100                                                                              100 100 100                                                                              100                                                                              100                                                                              60  --                             33F 95 100                                                                              80  100                                                                              90 100                                                                              100                                                                              100 100 100                                                                              70 100                                                                              40  --                             35F 70 90 40  100                                                                              -- 100                                                                              100                                                                              100 100 100                                                                              98 100                                                                              30  --                             36F 85 100                                                                              35  100                                                                              -- 20 100                                                                              100 100 100                                                                              100                                                                              100                                                                              15  --                             39F 100                                                                              100                                                                              85  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              90  100                            40F 100                                                                              100                                                                              30  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              90 100                                                                              75  --                             41F 100                                                                              100                                                                              35  90 70 100                                                                              90 100 100 100                                                                              50 100                                                                              70  --                             42F 45 100                                                                              50  100                                                                              70 55 80 100 100 100                                                                              70 100                                                                              75  100                            43F 25 80 15  98 35 0  20 100 100 100                                                                              100                                                                              100                                                                              60  95                             44F 0  15 0   65 0  0  0  70  100 100                                                                              40 100                                                                              0   100                            45F 0  75 35  70 35 0  60 50  85  100                                                                              50 100                                                                              75  70                             50F -- 40 0   75 45 40 60 100 100 95 30 -- 60  100                            __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE VII-F                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate - 0.56 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG JG                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNG CB                              __________________________________________________________________________    46F 25 35 20  50 35                                                                              35 0  20  75  100                                                                              35 95 --  50                              47F -- 75 25  90 40                                                                              25 80 100 100 100                                                                              80 -- 75  100                             48F -- 50 35  80 35                                                                              40 0  75  100 85 15 -- 50  75                              49F -- 35 0   75 30                                                                              0  20 100 100 100                                                                              80 -- 25  85                              51F -- 35 0   80 35                                                                              20 70 50  95  95 25 -- 65  50                              __________________________________________________________________________     (--) = Not Tested.                                                       

The compounds of the present invention and their salts are useful asherbicides and can be applied in a variety of ways at variousconcentrations. In practice, the compounds or salts are formulated intoherbicidal compositions, by admixture, in herbicidally effectiveamounts, with the adjuvants and carriers normally employed forfacilitating the dispersion of active ingredients for agriculturalapplications, recognizing the fact that the formulation and mode ofapplication of a toxicant may affect the activity of the materials in agiven application. Thus, these active herbicidal compounds or salts canbe formulated as granules of relatively large particle size, as wettablepowders, as emulsifiable concentrates, as powdery dusts, as flowables,as solutions or as any of several other known types of formulations,depending upon the desired mode of application. These formulations maycontain as little as about 0.5% to as much as about 95% or more byweight of active ingredient. A herbicidally effective amount dependsupon the nature of the seeds or plants to be controlled and the rate ofapplication varies from about 0.01 to approximately 10 pounds per acre,preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersants. The wettable powder isultimately applied to the soil either as a dry dust or as a dispersionin water or other liquid. Typical carriers for wettable powders includefuller's earth, kaolin clays, silicas and other readily wet organic orinorganic diluents. Wettable powders normally are prepared to containabout 5% to about 95% of the active ingredient and usually also containa small amount of wetting, dispersing, or emulsifying agent tofacilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which aredispersible in water or other dispersant, and may consist entirely ofthe active compound or salt with a liquid or solid emulsifying agent, ormay also contain a liquid carrier, such as xylene, heavy aromaticnaphthal, isophorone and other non-volatile organic solvents. Forherbicidal application, these concentrates are dispersed in water orother liquid carrier and normally applied as a spray to the area to betreated. The percentage by weight of the essential active ingredient mayvary according to the manner in which the composition is to be applied,but in general comprises about 0.5% to 95% of active ingredient byweight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relativelycoarse particles, are usually applied without dilution to the area inwhich suppression of vegetation is desired. Typical carriers forgranular formulations include sand, fuller's earth, attapulgite clay,bentonite clays, montmorillonite clay, vermiculite, perlite and otherorganic or inorganic materials which absorb or which may be coated withthe toxicant. Granular formulations normally are prepared to containabout 0.1% to about 25% of active ingredients which may includesurface-active agents such heavy aromatic naphthas, kerosene or otherpetroleum fractions, or vegetable oils; and/or stickers such asdextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents and adjuvants used inagricultural formulations include, for example, the alkyl and alkylarylsulfonates and sulfates and their salts; polyhydric alcohols;polyethoxylated alcohols, esters and fatty amines; and other types ofsurface-active agents, many of which are available in commerce. Thesurface-active agent, when used, normally comprises from 0.1% to 30% byweight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient withfinely divided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers for the toxicant,are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solidtoxicant in a liquid carrier such as water or oil, are employed forspecific purposes. These formulations normally contain about 5% to about95% of active ingredient by weight, and may also contain small amountsof a wetting, dispersing or emulsifying agent to facilitate dispersion.For application, the pastes are normally diluted and applied as a sprayto the area to be affected.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a dispersant in which it iscompletely soluble at the desired concentration, such as water, acetone,alkylated naphthalenes, xylene and other organic solvents. Pressurizedsprays, typically aerosols, wherein the active ingredient is dispersedin finely-divided form as a result of vaporization of a low boilingdispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to theplants in the conventional manner. Thus, the dust and liquidcompositions can be applied to the plant by the use of powder-dusters,boom and hand sprayers and spray dusters. The compositions can also beapplied from airplanes as a dust or a spray or by rope wick applicationsbecause they are effective in very low dosages. In order to modify orcontrol growth of germinating seeds or emerging seedlings, as a typicalexample, the dust and liquid compositions can be applied to the soilaccording to conventional methods and can be distributed in the soil toa depth of at least 1/20 inch below the soil surface. It is notnecessary that the phytotoxic compositions be mechanically admixed withthe soil particles since these compositions can also be applied merelyby spraying or sprinkling the surface of the soil. The phytotoxiccompositions of this invention can also be applied by addition toirrigation water supplied to the field to be treated. This method ofapplication permits the penetration of the compositions into the soil asthe water is absorbed therein. Dust compositions, granular compositionsor liquid formulations applied to the surface of the soil can bedistributed below the surface of the soil by conventional means such asdiscing, dragging or mixing operations. In the following examples theherbicidal compound can be substituted with the herbicidal salt of thecompound.

    __________________________________________________________________________    General Formula with Ranges                                                                    Specific Formula                                             __________________________________________________________________________    EMULSIFIABLE CONCENTRATE FORMULATIONS                                         Herbicidal compound                                                                       5-55    herbicidal compound                                                                        24                                           surfactant(s)                                                                             5-25    proprietary blend of oil-                                                                  10                                           solvent(s)  20-90   soluble sulfonates and                                                100%    polyoxyethylene ethers                                                        polar solvent                                                                              27                                                               petroleum hydrocarbon                                                                      39                                                                            100%                                         WETTABLE POWDER FORMULATIONS                                                  herbicidal compound                                                                        3-90   herbicidal compound                                                                        80                                           wetting agent                                                                             0.5-2   sodium dialkyl naphthalene                                                                 0.5                                          dispersing agent                                                                          1-8     sulfonate                                                 diluent(s)  8.5-87  sodium lignosulfonate                                                                      7                                                        100%    attapulgite clay                                                                           12.5                                                                          100%                                         EXTRUDED GRANULAR FORMULATIONS                                                herbicidal compound                                                                       1-20    herbicidal compound                                                                        10                                           binding agent                                                                             0-10    lignin sulfonate                                                                           5                                            diluent(s)  70-99   calcium carbonate                                                                          85                                                       100%                 100%                                         FLOWABLE FORMULATIONS                                                         herbicidal compound                                                                       20-70   herbicidal compound                                                                        45                                           surfactant(s)                                                                             1-10    polyoxyethylene ether                                                                      5                                            suspending agent(s)                                                                       0.05-1  attagel      0.05                                         antifreeze agent                                                                          1-10    propylene glycol                                                                           10                                           antimicrobial agent                                                                       1-10    1,2-benzisothiazoline-3-one                                                                0.03                                         antifoam agent                                                                            0.1-1   silicone defoamer                                                                          0.02                                         solvent     7.95-77.85                                                                            water        39.9                                                     100%                 100%                                         __________________________________________________________________________

When salts are used as the active ingredient in the herbicidalcompositions of this invention it is recommended to use salts that areagriculturally acceptable.

The phytotoxic compositions of this invention can also contain otheradditives, for example, fertilizers, other herbicides and otherpesticides, used as adjuvant or in combination with any of theabove-described adjuvants. Fertilizers useful in combination with theactive ingredients include, for example, ammonium nitrate, urea andsuperphosphate.

We claim:
 1. Compounds having the structural formula ##STR95## wherein Rand R¹ are hydrogen, C₁ -C₄ alkyl, R^(a) OC(O)--, where R^(a) is C₁ -C₄alkyl;R² is chlorine, bromine, or iodine; and R³, R⁴ and R⁵independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄haloalkyl; (9) R^(b) SO_(n) -- wherein R^(b) is C₁ -C₄ alkyl, C₁ -C₄haloalkyl, phenyl, benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e)independently are hydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or2; ##STR96## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen; (11)R^(f) C(O) wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁-C₄ alkoxy; (12) --NR^(g) R^(h) wherein R^(g) and R^(h) independentlyare hydrogen or C₁ -C₄ alkyl; or (13) R³ and R⁴ together can form a ringstructure with two adjacent carbon atoms of the phenyl ring; and theirsalts.
 2. The compounds of claim 1 wherein R and R¹ are hydrogen or C₁-C₄ alkyl; R² is chlorine, bromine, or iodine; R³ and R⁴ independentlyare hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, trifluoromethoxy,cyano, nitro, C₁ -C₄ haloalkyl, R^(b) SO_(n) wherein R^(b) is C₁ -C₄alkyl, C₁ -C₄ haloalkyl, phenyl, benzyl, --NR^(d) R^(e) wherein R^(d)and R^(e) independently are hydrogen and C₁ -C₄ alkyl; and n is theinteger 0, 1 or 2; R^(c) C(O)NH-- wherein R^(c) is C₁ -C₄ alkyl; R^(f)C(O)-- wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄alkoxy; or --NR^(g) R^(h) wherein R^(g) and R^(h) independently arehydrogen or C₁ -C.sub. 4 alkyl; and R⁵ is hydrogen and their salts. 3.The compounds of claim 1 wherein R and R¹ are hydrogen or methyl; R² ischlorine or bromine; R³ is hydrogen, chlorine, C₁ -C₄ alkoxy, R^(b)SO_(n) wherein R^(b) is C₁ -C₄ alkyl and n is the integer 0; R⁴ ishydrogen, chlorine, cyano, nitro, R^(b) SO_(n) wherein R^(b) is C₁ -C₄alkyl and n is 0 or 2, SO₂ N(CH₃)₂ or trifluoromethyl; and R⁵ ishydrogen and their salts.
 4. The compounds of claim 2 wherein R² ischlorine, R³ is substituted at the 3-position, and R⁴ is substituted atthe 4-position and their salts.
 5. The compounds of claim 3 wherein Rand R¹ are hydrogen; R² is chlorine; R³ is hydrogen, 3-chlorine,3-methoxy, 3-ethoxy or 3-n-propoxy and R⁴ is 4-chlorine, 4-bromine,4-CH₃ SO₂ -- or 4-C₂ H₅ SO₂ ; and R⁵ is hydrogen and their salts.
 6. Thecompounds of claim 1 wherein R and R¹ are hydrogen or C₁ -C₄ alkyl; R²is chlorine, bromine, or iodine or; R³ is hydrogen, halogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, nitro, C₁ -C₄ haloalkyl or R^(b) SO_(n) whereinR^(b) is C₁ -C₄ alkyl and n is the integer 0; R⁴ is hydrogen, halogen,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, cyano, nitro, C₁ -C₄ haloalkyl or R^(b)SO_(n) wherein R^(b) is C₁ -C₄ alkyl and n is the integer 0, 1 or 2; andR⁵ is hydrogen and their salts.
 7. The compounds of claim 1 wherein Rand R¹ are hydrogen or methyl; R² is chlorine, bromine, or iodine; R³ ishydrogen, halogen, methyl, C₁ -C₄ alkoxy, nitro, trifluoromethyl ormethylthio; R⁴ is hydrogen, halogen, methyl, methoxy, cyano, nitro,trifluoromethyl, methylthio or CH₃ SO₂ ; and R⁵ is hydrogen and theirsalts.
 8. The compounds of claim 6 wherein R³ is in the 3-position andR⁴ is in the 4-position and their salts.
 9. The compounds of claim 7wherein R³ is in the 3-position and R⁴ is in the 4-position and theirsalts.
 10. The compounds of claim 1 wherein R and R¹ are hydrogen or C₁-C₄ alkyl; R² is chlorine, bromine, or iodine or; R³ is hydrogen,halogen, C₁ -C₄ alkoxy, or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyland n is the integer 0; R⁴ is R^(b) SO_(n) -- wherein R^(b) is C₁ -C₄alkyl and n is the integer 2; and R⁵ is hydrogen.
 11. The compounds ofclaim 1 wherein R and R¹ are hydrogen or methyl; R² is chlorine orbromine; R³ is hydrogen, halogen, methoxy or methylthio; R⁴ is R^(b)SO_(n) -- wherein R^(b) is methyl and n is the integer 2; and R⁵ ishydrogen.
 12. The compounds of claim 10 wherein R³ is in the 3-positionand R⁴ is in the 4-position.
 13. The compounds of claim 11 wherein R³ isin the 3-position and R⁴ is in the 4-position.
 14. The compound of claim1 wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is hydrogen,R⁴ is 4-chlorine and R⁵ is hydrogen and its salts.
 15. The compound ofclaim 1 wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is3-chlorine, R⁴ is 4-chlorine and R⁵ is hydrogen and its salts.
 16. Thecompound of claim 1 wherein R is hydrogen, R¹ is hydrogen, R² ischlorine, R³ is 3-chlorine, R⁴ is 4-methoxy and R⁵ is hydrogen and itssalts.
 17. The compound of claim 1 wherein R is hydrogen, R¹ ishydrogen, R² is chlorine, R³ is hydrogen, R⁴ is 4-bromine and R⁵ ishydrogen and its salts.
 18. The compound of claim 1 wherein R ishydrogen, R¹ is hydrogen, R² is chlorine, R³ is hydrogen, R⁴ is 4-CH₃SO₂ and R⁵ is hydrogen and its salts.
 19. The sodium, isopropylamine,triethylamine and potassium salts of the compound of claim
 15. 20. Themethod of controlling undesirable vegetation comprising applying to thearea where control is desired, an herbicidally effective amount of acompound having the formula ##STR97## whereinR and R¹ are hydrogen, C₁-C₄ alkyl, R^(a) OC(O)--, where R^(a) is C₁ -C₄ alkyl; R² is chlorine,bromine, iodine or C₁ -C₄ alkoxy; and R³, R⁴ and R⁵ independently are(1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5)trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b)SO_(n) -- wherein R^(b) is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, phenyl,benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently arehydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2; ##STR98##wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen; (11) R^(f) C(O)wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄alkoxy; (12) --NR^(g) R^(h) wherein R^(g) and R^(h) independently arehydrogen or C₁ -C₄ alkyl; or (13) R³ and R⁴ together can form a ringstructure with two adjacent carbon atoms of the phenyl ring; and theirsalts.
 21. The method of claim 20 wherein R and R¹ are hydrogen or C₁-C₄ alkyl; R² is chlorine, bromine, iodine or C₁ -C₄ alkoxy; R³ and R⁴independently are hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,trifluoromethoxy; cyano, nitro, C₁ -C₄ haloalkyl, R^(b) SO_(n) whereinR^(b) is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, phenyl, benzyl, --NR^(d) R^(e)wherein R^(d) and R^(e) independently are hydrogen and C₁ -C₄ alkyl; andn is the integer 0, 1 or 2; R^(c) C(O)NH-- wherein R^(c) is C₁ -C₄alkyl; R^(f) C(O)-- wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₂ -C₄haloalkyl, C₁ -C₄ alkoxy; or --NR^(g) R^(h) wherein R^(g) and R^(h)independently are hydrogen or C₁ -C₄ alkyl; and R⁵ is hydrogen and theirsalts.
 22. The method of claim 20 wherein R and R¹ are hydrogen ormethyl; R² is chlorine or bromine; R³ is hydrogen, chlorine, C₁ -C₄alkoxy, R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl and n is the integer0; R⁴ is hydrogen, chlorine, cyano, nitro, R^(b) SO_(n) wherein R^(b) isC₁ -C₄ alkyl and n is 0 or 2, SO₂ N(CH₃)₂ or trifluoromethyl; and R⁵ ishydrogen and their salts.
 23. The method of claim 21 wherein R² ischlorine, R³ is substituted at the 3-position, and R⁴ is substituted atthe 4-position and their salts.
 24. The method of claim 20 wherein R andR¹ are hydrogen; R² is chlorine; R³ is hydrogen, 3-chlorine, 3-methoxy,3-ethoxy or 3-n-propoxy and R⁴ is 4-chlorine, 4-bromine, 4-CH₃ SO₂ -- or4-C₂ H₅ SO₂ ; and R⁵ is hydrogen and their salts.
 25. The method ofclaim 20 wherein R an R¹ are hydrogen or C₁ -C₄ alkyl; R² is chlorine,bromine, iodine or C₁ -C₄ alkoxy; R³ is hydrogen, halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, nitro, C₁ -C₄ haloalkyl or R^(b) SO_(n) wherein R^(b) isC₁ -C₄ alkyl and n is the integer 0; R⁴ is hydrogen, halogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, cyano, nitro, C₁ -C₄ haloalkyl or R^(b) SO_(n)wherein R^(b) is C₁ -C₄ alkyl and n is the integer 0, 1 or 2; and R⁵ ishydrogen and their salts.
 26. The method of claim 20 wherein R and R¹are hydrogen or methyl; R² is chlorine, bromine, iodine or methoxy; R³is hydrogen, halogen methyl, C₁ -C₄ alkoxy, nitro, trifluoromethyl ormethylthio; R⁴ is hydrogen, halogen, methyl, methoxy, cyano, nitro,trifluoromethyl, methylthio or CH₃ SO₂ ; and R⁵ is hydrogen and theirsalts.
 27. The method of claim 25 wherein R³ is in the 3-position and R⁴is in the 4-position and their salts.
 28. The method of claim 26 whereinR³ is in the 3-position and R⁴ is in the 4-position and their salts. 29.The method of claim 20 wherein R and R¹ are hydrogen or C₁ -C₄ alkyl; R²is chlorine, bromine, iodine or C₁ -C₄ alkoxy; R³ is hydrogen, halogen,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, nitro, C₁ -C₄ haloalkyl or R^(b) SO_(n)wherein R^(b) is C₁ -C₄ alkyl and n is the integer 0; R⁴ is R^(b) SO_(n)-- wherein R^(b) is C₁ -C₄ alkyl and n is the integer 2; and R⁵ ishydrogen and their salts.
 30. The method of claim 20 wherein R and R¹are hydrogen or methyl; R² is chlorine, bromine, iodine or methoxy; R³is hydrogen, halogen, methyl, methoxy, nitro, trifluoromethyl, ormethylthio; R⁴ is R^(b) SO_(n) -- wherein R^(b) is methyl and n is theinteger 2; and R⁵ is hydrogen and their salts.
 31. The method of claim29 wherein R³ is in the 3-position and R⁴ is in the 4-position and theirsalts.
 32. The method of claim 30 wherein R³ is in the 3-position and R⁴is in the 4-position and their salts.
 33. The method of claim 20 whereinR is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is hydrogen, R⁴ is4-chlorine and R⁵ is hydrogen and its salts.
 34. The method of claim 20wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-chlorine,R⁴ is 4-chlorine and R⁵ is hydrogen and its salts.
 35. The method ofclaim 20 wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ ishydrogen, R⁴ is 4-bromine and R⁵ is hydrogen and its salts.
 36. Themethod of claim 20 wherein R is hydrogen, R¹ is hydrogen, R² ischlorine, R³ is hydrogen, R⁴ is 4-CH₃ SO₂ and R⁵ is hydrogen and itssalts.
 37. The method of claim 34 wherein the salts are the sodium,isopropylamine, triethylamine and potassium salts.
 38. An herbicidalcomposition comprising an herbicidally active 2-(2-chlorine, bromine,iodine or C₁ -C₄ alkoxy)benzoyl-1,3-cyclohexanedione or its salts and aninert carrier therefor.
 39. The herbicidal composition of claim 38wherein the 2-position of the benzoyl moiety is substituted withchlorine, bromine or C₁ -C₄ alkoxy.
 40. The herbicidal composition ofclaim 39 wherein the 2-position of the benzoyl moiety is substitutedwith chlorine, bromine or methoxy.
 41. The herbicidal composition ofclaim 38 wherein the 2-position of the benzoyl moiety is substitutedwith chlorine, bromine or C₁ -C₄ alkoxy and the 5-position of the1,3-cyclohexanedione moiety is substituted with one or two C₁ -C₄ alkylgroups.
 42. The herbicidal composition of claim 38 wherein the2-position of the benzoyl moiety is substituted with chlorine, bromine,iodine or methoxy and the 5-position of the 1,3-cyclohexanedione moietyis substituted with one or two methyl groups.
 43. The compound of claim1 wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is3-chlorine, R⁴ is 4-C₂ H₅ SO₂, and R⁵ is hydrogen and its salts.
 44. Thecompound of claim 1 wherein R is hydrogen, R¹ is hydrogen, R² is ischlorine, R³ is 3-methoxy, R⁴ is 4-CH₃ SO₂, R⁵ is hydrogen and itssalts.
 45. The compound of claim 1 wherein R is hydrogen, R¹ ishydrogen, R² is chlorine, R³ is 3-chlorine, R⁴ is 4-n-C₃ H₇ SO₂, and R⁵is hydrogen and its salts.
 46. The compound of claim 1 wherein R ishydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-methoxy, R⁴ is4-bromine and R⁵ is hydrogen and its salts.
 47. The compound of claim 1wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-ethoxy,R⁴ is 4-C₂ H₅ SO₂ and R⁵ is hydrogen and its salts.
 48. The compound ofclaim 1 wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is3-methoxy, R⁴ is 4-C₂ H₅ SO₂ and R⁵ is hydrogen and its salts.
 49. Thecompound of claim 1 wherein R is hydrogen, R¹ is hydrogen, R² ischlorine, R³ is 3-n-C₃ H₇ O, R⁴ is 4-C₂ H₅ SO₂ and R⁵ is hydrogen andits salts.
 50. The compound of claim 1 wherein R is hydrogen, R¹ ishydrogen, R² is chlorine, R³ is 3-n-C₃ H₇ O, R⁴ is 4-CH₃ SO₂ and R⁵ ishydrogen and its salts.
 51. The compound of claim 1 wherein R ishydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-ethylthio, R⁴ is 4-C₂H₅ SO₂ and R⁵ is hydrogen and its salts.
 52. The compound of claim 1wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-n-C₄ H₉O, R⁴ is 4-C₂ H₅ SO₂, and R⁵ is hydrogen and its salts.
 53. The compoundof claim 1 wherein R is hydrogen, R¹ is hydrogen, R² is is chlorine, R³is hydrogen, R⁴ is 4-methylthio, R⁵ is hydrogen and its salts.
 54. Themethod of claim 20 wherein R is hydrogen, R¹ is hydrogen, R² ischlorine, R³ is 3-chlorine, R⁴ is 4-C₂ H₅ SO₂ and R⁵ is hydrogen and itssalts.
 55. The method of claim 20 wherein R is hydrogen, R¹ is hydrogen,R² is chlorine, R³ is 3-methoxy, R⁴ is 4-CH₃ SO₂ and R⁵ is hydrogen andits salts.
 56. The method of claim 20 wherein R is hydrogen, R¹ ishydrogen, R² is chlorine, R³ is 3-chlorine, R⁴ is 4-n-C₃ H₇ SO₂ and R⁵is hydrogen and its salts.
 57. The method of claim 20 wherein R ishydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-methoxy, R⁴ is4-bromine and R⁵ is hydrogen and its salts.
 58. The method of claim 20wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-ethoxy,R⁴ is 4-C₂ H₅ SO₂, R⁵ is hydrogen and its salts.
 59. The method of claim20 wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is3-methoxy, R⁴ is 4-C₂ H₅ SO₂ and R⁵ is hydrogen and its salts.
 60. Themethod of claim 20 wherein R is hydrogen, R¹ is hydrogen, R² ischlorine, R³ is 3-n-C₃ H₇ O, R⁴ is 4-C₂ H₅ SO₂ and R⁵ is hydrogen andits salts.
 61. The method of claim 20 wherein R is hydrogen, R¹ ishydrogen, R² is chlorine, R³ is 3-n-C₃ H₇ O, R⁴ is 4-CH₃ SO₂ and R⁵ ishydrogen and its salts.
 62. The method of claim 20 wherein R ishydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-ethylthio, R⁴ is 4-C₂H₅ SO₂ and R⁵ is hydrogen and its salts.
 63. The method of claim 20wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ is 3-n-C₄ H₉O, R⁴ is 4-C₂ H₅ SO₂ and R⁵ is hydrogen and its salts.
 64. The method ofclaim 20 wherein R is hydrogen, R¹ is hydrogen, R² is chlorine, R³ ishydrogen, R⁴ is 4-methylthio and R⁵ is hydrogen and its salts.